CN108063221A

CN108063221A - Prepare method, negative material, cathode pole piece and the lithium ion battery of negative material

Info

Publication number: CN108063221A
Application number: CN201710328726.1A
Authority: CN
Inventors: 李慧; 雷丹; 夏圣安
Original assignee: Huawei Technologies Co Ltd
Current assignee: Huawei Technologies Co Ltd
Priority date: 2017-05-11
Filing date: 2017-05-11
Publication date: 2018-05-22

Abstract

This application provides a kind of method for preparing negative material, negative material, cathode pole piece and lithium ion batteries.The method for preparing negative material includes：Inner nuclear material and the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element are mixed and heated；The inner nuclear material that this is coated with to the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element is mixed and heated with functionalization graphene；By the functionalization graphene, should the polymer containing miscellaneous element or ionic liquid containing miscellaneous element and the inner nuclear material be sintered, obtain the negative material that graphene fixation is coated on to the inner nuclear material surface by doped carbon.The method for preparing negative material that the application provides obtains the negative material that doped carbon fixes graphene coated inner nuclear material in a manner that doped carbon fixes graphene, graphene can be made to be stably fixed on inner nuclear material surface, avoid the reunion of graphene.

Description

Prepare method, negative material, cathode pole piece and the lithium ion battery of negative material

Technical field

This application involves field of lithium ion battery, and more particularly, to a kind of method for preparing negative material, cathode Material, cathode pole piece and lithium ion battery.

Background technology

With the popularization of electronic product in recent years, as the lithium battery of its power supply, because with light weight, small, work It the advantages that voltage height, energy density height, output power, charge efficiency height and memory-less effect, is increasingly taken seriously.But by In the bottleneck for being limited by lithium ion battery energy density, it is subject to constantly denouncing for user.In view of lithium ion battery energy density Bottleneck has been not easy to break through, and therefore, researcher is using the rapid charge characteristic of lithium ion battery as current main research at present The demand that the performance of battery is allowed to closely follow development in science and technology is made great efforts in direction.

As currently most dazzling concept material, graphene has benefited from its high power capacity always, high conductivity and can be fast The performances such as speed charging occupy a tiny space in lithium battery material research.But graphene but has that specific surface area is huge, easily rolls into a ball The defects of poly-, if applying in lithium ion battery, can cause battery to reduce, and obstruct lithium ion transport, for the first time efficiency Lowly, the problems such as electrode slice can not be prepared can't produce commercialization at present.

Patent US8580432B2, which is provided, has used a kind of negative material, and this application is by nano-graphene piece, nanometer cathode Material and carbon source material mixing granulation, are then carbonized, and obtain the outside nano-graphene of carbon coated and of nanometer anode material Grain, but graphene is still disorder distribution within this material so that the specific surface area of material is huge, is not easy to be prepared into pole piece, Meanwhile graphene is fixed without chemical bond so that material can not be used because of the reunion of graphene, and battery life is subject to seriously It influences.

In the negative material of current lithium ion battery, graphene remains reunion, so as to the confusion of graphene Distribution and reunion cause the specific surface area of battery huge, obstruct lithium ion transport, cause the charge rate of battery relatively slow and use The problem of service life is low,

The content of the invention

The application provides a kind of method for preparing negative material, negative material, cathode pole piece and lithium ion battery, can solve The agglomeration traits of graphene when certainly the negative material is as battery cathode, so as to extend the service life of battery and improve battery Charge rate.

In a first aspect, providing a kind of method for preparing negative material, this method includes：By inner nuclear material with containing miscellaneous member The polymer of element or the ionic liquid containing miscellaneous element are mixed and heated, so as to be somebody's turn to do the polymer containing miscellaneous element or contain miscellaneous member The ionic liquid of element coats the inner nuclear material；This is coated with the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element Inner nuclear material be mixed and heated with functionalization graphene so that the functionalization graphene coats the polymer for containing miscellaneous element Or ionic liquid and the inner nuclear material containing miscellaneous element；By the functionalization graphene, should containing miscellaneous element polymer or Ionic liquid containing miscellaneous element and the inner nuclear material are sintered, and obtain and graphene is fixed cladding by doped carbon The negative material on the inner nuclear material surface.

The method for preparing negative material that first aspect provides, first by inner nuclear material and polymerizeing or containing containing miscellaneous element The ionic liquid for having miscellaneous element carries out cladding processing, then by functionalization graphene with being coated with the polymer containing miscellaneous element Or the chemical reaction between the ionic liquid inner nuclear material containing miscellaneous element, by functionalization graphene and it is coated on inner nuclear material The ionic liquid containing miscellaneous element or polymer or containing miscellaneous element between it is fixed contain so that the functionalization graphene coats this There are the polymer of miscellaneous element or the ionic liquid containing miscellaneous element and the inner nuclear material, by the functionalization graphene, this contains The polymer of miscellaneous element or ionic liquid containing miscellaneous element and the inner nuclear material are sintered, and acquisition passes through doped carbon Graphene fixation is coated on to the negative material on the inner nuclear material surface.The negative material obtained using this method, can make Graphene is stably fixed on inner nuclear material surface, avoids the reunion of graphene, so as to avoid the confusion distribution of graphene With reunion and cause that the specific surface area of the lithium ion battery prepared by the negative material is huge, barrier lithium ion transport and using the longevity The problem of life reduces.Material has both fast charge and the characteristic of high-energy density, and is readily produced and commercial.

In a kind of possible realization method of first aspect, the polymer that should contain miscellaneous element can be by containing miscellaneous element Organic monomer obtained by polymerisation, this by inner nuclear material with containing miscellaneous element mixed with polymers and heating so that should Polymer containing miscellaneous element or the ionic liquid containing miscellaneous element coat the inner nuclear material, including：By the inner nuclear material with being somebody's turn to do Organic monomer containing miscellaneous element is mixed and heated, and contains the organic monomer of miscellaneous element on the inner nuclear material surface by this Polymerisation generates the polymer for containing miscellaneous element, so as to should contain the polymer overmold of the miscellaneous element inner nuclear material..

In a kind of possible realization method of first aspect, the functionalization graphene and the polymer that miscellaneous element should be contained It or should be containing being the functional group that is carried by the functionalization graphene between the ionic liquid of miscellaneous element and should be containing miscellaneous element Polymerization or the chemical reaction being somebody's turn to do between the functional group that the ionic liquid containing miscellaneous element carries are fixed.

In a kind of possible realization method of first aspect, the quality that feeds intake of the inner nuclear material accounts for the inner nuclear material, is somebody's turn to do Polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, the functionalization graphene feed intake quality sum 79.9%~ 98.9%, the quality that feeds intake of the functionalization graphene accounts for the inner nuclear material, should contain the polymer of miscellaneous element or containing miscellaneous element Ionic liquid, the functionalization graphene feed intake the 0.1%~10% of quality sum, polymer containing miscellaneous element or should contain The quality that feeds intake of the ionic liquid of miscellaneous element accounts for the inner nuclear material, should contain the polymer of miscellaneous element or the ion containing miscellaneous element Liquid, the functionalization graphene feed intake the 1%~20% of quality sum.

In a kind of possible realization method of first aspect, the functional group which carries includes：Amino Functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitre In base functional group, sulfonate functional groups, ester functional groups, itrile group functional group, azo group functional group and siloxy group functional group It is at least one.

In a kind of possible realization method of first aspect, should containing miscellaneous element polymer or containing miscellaneous element from The functional group that sub- liquid carries includes：Amido functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxyl-functional Group, keto functional group, carbonyl functional group, nitro functions, sulfonate functional groups, ester functional groups, itrile group functional group and azo At least one of base functional group.

In a kind of possible realization method of first aspect, which includes：Graphite, hard carbon, soft carbon, silicon, oxygen The conjunction of SiClx, silicon-carbon compound, lithium titanate, silicon alloy, germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, titanium and above-mentioned metal material At least one of mixture of golden, above-mentioned metal material oxide and above-mentioned material.

In a kind of possible realization method of first aspect, should containing miscellaneous element polymer or containing miscellaneous element from Miscellaneous element in sub- liquid includes：At least one of nitrogen, phosphorus, boron, oxygen, sulphur, fluorine, chlorine and protium.

In a kind of possible realization method of first aspect, the quality of the miscellaneous element accounts for the polymer for containing miscellaneous element Or the 1%~60% of the quality of the ionic liquid containing miscellaneous element.

In a kind of possible realization method of first aspect, it should include containing the polymer of miscellaneous element：Sila ring (thiophene Cough up) in polymer, thia ring (thiophene) polymer, organophosphorus polymer, organo-boron polymer and nitrogenous (pyrroles) polymer It is at least one.

In a kind of possible realization method of first aspect, it should include containing the organic monomer of miscellaneous element：Thiophene cough up monomer, At least one of thiophene monomer, phosphonic acids ester monomer, boric acid ester monomer and nitrogen containing monomer.

In a kind of possible realization method of first aspect, it should include containing the ionic liquid of miscellaneous element：Triphenyl borine, 3- methyl-butvl pyridine dicyan amine salt, 1- butyl -3- methylimidazole dicyan amine salt, dialkylimidazolium organic sulfonic acid and 1- ethyls - At least one of 3- methylimidazole cdicynanmides.

In a kind of possible realization method of first aspect, which includes：Doped graphene and oxidation At least one of graphene.

In a kind of possible realization method of first aspect, the doped chemical in the doped graphene includes：Nitrogen, phosphorus, At least one of boron, oxygen, sulphur, fluorine, chlorine and protium.

Second aspect provides a kind of negative material, which includes inner nuclear material and be distributed in the kernel material Expect the articulamentum and clad on surface, which is connected with the inner nuclear material by the articulamentum, which is uniform point Cloth the laminated structure of the inner nuclear material periphery graphene, the articulamentum include doped carbon, a part for the doped carbon with should Kernel adhesion, another part of the doping carbon particle are connected with the graphene by carbonnitrogen bond.

The negative material that second aspect provides, the graphene of the clad are to fix cladding by the doped carbon of the articulamentum On the inner nuclear material surface, graphene can be made to be stably fixed on inner nuclear material surface, avoid the reunion of graphene, Confusion so as to avoid graphene is distributed and reunites and cause the specific surface area of the lithium ion battery prepared by the negative material The problem of huge, barrier lithium ion transport and service life reduce, which has both fast charge and the characteristic of high-energy density.

In a kind of possible realization method of second aspect, should containing miscellaneous element polymer or containing miscellaneous element from Sub- liquid is coated and fixed by heating melting in the inner nuclear material periphery, so as to pass through bag between the clad and the inner nuclear material The doped carbon containing the carbonnitrogen bond is fixedly connected.

In a kind of possible realization method of second aspect, the functional group which carries includes：Amido functional group, Amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro function At least one in group, sulfonate functional groups, ester functional groups, itrile group functional group, azo group functional group and siloxy group functional group Kind.

In a kind of possible realization method of second aspect, the polymer containing miscellaneous element or contain miscellaneous element The functional group that ionic liquid carries includes：Amido functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxyl official It can group, keto functional group, carbonyl functional group, nitro functions, sulfonate functional groups, ester functional groups, itrile group functional group and idol At least one of Dan Ji functional groups.

In a kind of possible realization method of second aspect, which includes：Graphite, hard carbon, soft carbon, silicon, oxygen The conjunction of SiClx, silicon-carbon compound, lithium titanate, silicon alloy, germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, titanium and above-mentioned metal material At least one of mixture of golden, above-mentioned metal material oxide and above-mentioned material.

In a kind of possible realization method of second aspect, should containing miscellaneous element polymer or containing miscellaneous element from Miscellaneous element in sub- liquid includes：At least one of nitrogen, phosphorus, boron, oxygen, sulphur, fluorine, chlorine and protium.

In a kind of possible realization method of second aspect, the quality of the miscellaneous element accounts for the polymer for containing miscellaneous element Or the 1%~60% of the quality of the ionic liquid containing miscellaneous element.

In a kind of possible realization method of second aspect, it should include containing the polymer of miscellaneous element：Sila ring (thiophene Cough up) in polymer, thia ring (thiophene) polymer, organophosphorus polymer, organo-boron polymer and nitrogenous class (pyrroles) polymer At least one.

In a kind of possible realization method of second aspect, the polymer that should contain miscellaneous element can be by containing miscellaneous element Organic monomer obtain, should include containing organic monomer of miscellaneous element：Thiophene coughs up monomer, thiophene monomer, phosphonic acids ester monomer, borate At least one of monomer and nitrogen containing monomer.

It, should the ionic liquid bag containing miscellaneous element containing miscellaneous element in a kind of possible realization method of second aspect It includes：Triphenyl borine, 3- methyl-butvl pyridine dicyan amine salt, 1- butyl -3- methylimidazole dicyan amine salt, dialkylimidazolium are organic At least one of sulfonic acid and 1- ethyl-3-methylimidazole cdicynanmides.

In a kind of possible realization method of second aspect, which includes：Doped graphene and graphene oxide At least one of.

In a kind of possible realization method of second aspect, the doped chemical in the doped graphene includes：Nitrogen, phosphorus, At least one of boron, oxygen, sulphur, fluorine, chlorine and protium.

The third aspect provides a kind of cathode pole piece, which includes collector and coated on the collector Negative material in above-mentioned second aspect and its various realization methods.

The cathode pole piece that the third aspect provides, can make the graphene in negative material be stably fixed to inner nuclear material On, the reunion of graphene is avoided, lithium ion transport and use can be obstructed by solving the lithium ion battery prepared by the cathode pole piece The problem of service life reduction.

Fourth aspect provides a kind of lithium ion battery, the lithium ion battery include cathode pole piece, anode pole piece, membrane, Nonaqueous electrolytic solution and shell, wherein, which includes collector and coated in the above-mentioned second aspect on the collector And its negative material in various realization methods.

The lithium ion battery that fourth aspect provides, the negative material on cathode pole piece can be stably fixed to graphene On inner nuclear material, the reunion of graphene is avoided, the confusion so as to avoid graphene is distributed and reunites and cause battery specific surface The problem of long-pending huge, barrier lithium ion transport and service life reduce, improves the charge rate of the lithium ion battery and using the longevity Life, and be readily produced and commercial.

Description of the drawings

Fig. 1 is the schematic diagram of the structure of the negative material of one embodiment of the invention.

Fig. 2 is that the polymer of one embodiment of the invention fixes the stereoscan photograph of graphene coated graphite material.

Fig. 3 is that the doped carbon of one embodiment of the invention fixes the stereoscan photograph of graphene coated graphite material.

Fig. 4 is that the doped carbon of one embodiment of the invention fixes the transmission electron microscope photo of graphene coated graphite material.

Fig. 5 is the stereoscan photograph of the doped carbon coated graphite material of one embodiment of the invention.

Fig. 6 is that the doped carbon of one embodiment of the invention fixes the stereoscan photograph of graphene coated graphite material.

Fig. 7 is the stereoscan photograph of the doped carbon coated graphite admixed graphite alkene material of one embodiment of the invention.

Fig. 8 is that the doped carbon of one embodiment of the invention fixes the transmission electron microscope photo of graphene coated graphite material.

Specific embodiment

Below in conjunction with attached drawing, the technical solution of the application is described.

The basic theories scheme of quick charge includes two, first, structure ion transmission channel, accelerates the transmission of ion；Two It is the energy barrier for reducing lithium ion insertion negative material.But both schemes can all be faced with energy density reduction and material The problem of electric conductivity reduces.Graphene has high power capacity, high conductivity and can be with performances such as quick charges, in lithium battery material It occupies a tiny space in material research.But graphene but has the defects of specific surface area is huge, easily reunites, and applies in lithium-ion electric Chi Zhong can obstruct lithium ion transport, and the charge rate for causing battery is slower, and service efficiency is low for the first time, and electrode slice can not be prepared The problems such as, can battery be reduced.

The problem of reunion can be generated in lithium battery by being applied based on graphene, obstruction lithium ion transport, this application provides A kind of method for preparing negative material, the negative material prepared using this method can be stably fixed to graphene interior On nuclear material surface, the reunion of graphene is avoided, the confusion so as to avoid graphene is distributed and reunites and cause by the cathode The problem of specific surface area of the lithium ion battery of material preparation is huge, barrier lithium ion transport and service life reduce.

The preparation method of the negative material provided below the application is described in detail, the specific steps bag of this method It includes：

Step 110, inner nuclear material is mixed simultaneously with the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element Heating, so that the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element coat the inner nuclear material.

Specifically, in step 110, by inner nuclear material with containing miscellaneous element polymer or containing miscellaneous element from Sub- liquid is mixed and heated, for example, protective gas can be passed through in kettle is coated, the protective gas can be nitrogen or its His inert gas, and cladding processing is carried out at 100~250 DEG C, so as to which polymer containing miscellaneous element or miscellaneous element should be contained Ionic liquid coat the inner nuclear material, that is, obtain be coated with the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element Inner nuclear material.

Step 120, the inner nuclear material of the polymer for containing miscellaneous element or ionic liquid containing miscellaneous element will be coated with It is mixed and heated with functionalization graphene, so that the functionalization graphene coats the polymer for containing miscellaneous element or containing miscellaneous member The ionic liquid and the inner nuclear material of element.

Specifically, the inner nuclear material of the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element will be coated with It is mixed and heated with functionalization graphene, for example, by the two after mixing, protective gas, example can be passed through in kettle is coated Such as, can be nitrogen or other inert gases, and cladding processing is carried out at 100~250 DEG C so that functionalization graphene with Polymer containing miscellaneous element or the ionic liquid containing miscellaneous element react, and functionalization graphene is made uniformly to be fixed to On polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, acquisition is coated with the functionalization graphene and is coated with this The inner nuclear material of polymer containing miscellaneous element or the ionic liquid containing miscellaneous element contains so that the functionalization graphene coats this There are the polymer of miscellaneous element or the ionic liquid containing miscellaneous element and the inner nuclear material.It obtains interior with two layers clad Nuclear material.And it is to pass through chemistry between functionalization graphene and the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element React fixed, functionalization graphene refers to the graphene containing particular functional group.

Step 130, by the functionalization graphene, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element and The inner nuclear material is sintered, and obtains the cathode material that graphene fixation is coated on to the inner nuclear material surface by doped carbon Material.

Specifically, by the functionalization graphene, the polymer containing miscellaneous element or the ion containing miscellaneous element of acquisition Liquid and the inner nuclear material are sintered, and obtain and graphene fixation is coated on the inner nuclear material surface by doped carbon Negative material.The inner nuclear material with two layers of clad that will be obtained is placed in the sintering equipment of inert atmosphere protection, high Temperature sintering, at 500 DEG C~1300 DEG C, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element are burnt for sintering temperature control Form for doped carbon, the functionalization graphene of outer layer is sintered into graphene, that is, after being sintered, carries the function fossil of functional group Black alkene becomes not carrying the graphene of functional group, obtains that graphene fixation is coated on the inner nuclear material surface by doped carbon Negative material.

The method provided in an embodiment of the present invention for preparing negative material, first by inner nuclear material and the polymer containing miscellaneous element Or the ionic liquid containing miscellaneous element is mixed and heated, make this contain the polymer of miscellaneous element or containing miscellaneous element from Sub- liquid coats the inner nuclear material, then by functionalization graphene with being coated with the polymer containing miscellaneous element or containing miscellaneous element Ionic liquid inner nuclear material be mixed and heated, by functionalization graphene with containing miscellaneous element or polymer or containing miscellaneous element Ionic liquid is fixed, make the functionalization graphene coat the polymer for containing miscellaneous element or ionic liquid containing miscellaneous element with And the inner nuclear material, finally by the functionalization graphene, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element And the inner nuclear material is sintered, and obtains being coated on graphene fixation by doped carbon the cathode on inner nuclear material surface Material.The negative material obtained using this method is obtained doped carbon in a manner that doped carbon fixes graphene and fixes graphite Alkene coats the negative material of inner nuclear material, and graphene can be made to be stably fixed on inner nuclear material surface, avoid graphene Reunite, the confusion so as to avoid graphene is distributed and reunites and cause the ratio table of the lithium ion battery prepared by the negative material The problem of area is huge, barrier lithium ion transport and service life reduce.Material has both fast charge and the characteristic of high-energy density, and It is readily produced and commercial.

Optionally, as one embodiment, since the polymer for containing miscellaneous element can be by containing the organic of miscellaneous element Monomer is obtained by polymerisation, in step 110, by inner nuclear material with containing miscellaneous element mixed with polymers and heating, with This is made to contain the polymer overmold of the miscellaneous element inner nuclear material, including：

The inner nuclear material and the organic monomer containing miscellaneous element are mixed and heated, organic list of miscellaneous element is contained by this Polymerisation of the body on the inner nuclear material surface generates the polymer for containing miscellaneous element, so that should the polymerization containing miscellaneous element Object coats the inner nuclear material.

Specifically, since the polymer for containing miscellaneous element can be anti-by polymerizeing by the organic monomer for containing miscellaneous element It should obtain, therefore, this can be contained to the organic monomer and inner nuclear material of miscellaneous element, be dispersed in reaction solution, add catalyst And heat, the organic monomer containing miscellaneous element is made to generate polymer by polymerisation on inner nuclear material, is then filtered, is done It is dry, so that should be containing the polymer overmold of the miscellaneous element inner nuclear material to get to being coated in the polymer containing miscellaneous element Nuclear material.

Optionally, as one embodiment, in the step 120, the functionalization graphene was with that should contain polymerizeing for miscellaneous element It is the functional group that is carried by the functionalization graphene between object or ionic liquid containing miscellaneous element and should be containing miscellaneous element Chemical reaction between the functional group that polymerization or ionic liquid containing miscellaneous element carry is fixed.

It specifically, should the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element before doped carbon is generated It is coated on the inner nuclear material surface, by containing the polymer of miscellaneous element or ionic liquid containing miscellaneous element carries Chemical reaction between the functional group that functional group and functionalization graphene carry, by functionalization graphene fixation be coated with containing On the inner nuclear material of the polymer of miscellaneous element or ionic liquid containing miscellaneous element, functionalization graphene is made to consolidate by Multipoint Uniform Determine onto the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, and this contains polymer of miscellaneous element or containing miscellaneous The ionic liquid of element is coated on inner nuclear material surface, has the functionalization graphene, internal layer so as to obtain external sheath It is coated with the inner nuclear material of the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element.

Optionally, the functionalization graphene carry functional group and should containing miscellaneous element polymerization or containing miscellaneous element from Chemical reaction between the functional group of the carrying of sub- liquid can be that hydrogen bond attracts reaction and/or condensation reaction.

The condensation reaction can include aldimine condensation reaction, aldol reaction, Nuo Wengeer (knoevenagel) condensations Reaction, Clarkson (claisen) condensation reaction, Wittig (wittig) reaction in any one or a few.

It is to be understood that the functionalization graphene carry functional group and should containing miscellaneous element polymerization or containing miscellaneous element from Chemical reaction between the functional group of the carrying of sub- liquid can also be other kinds of chemical reaction.The condensation reaction can be with Including other condensation reactions, this is not restricted for the embodiment of the present invention.

In the preparation method, the quality that feeds intake of the inner nuclear material accounts for the inner nuclear material, the polymer that should contain miscellaneous element Or ionic liquid, functionalization graphene containing miscellaneous element feed intake the 79.9%~98.9% of quality sum, the function fossil The quality that feeds intake of black alkene accounts for the inner nuclear material, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, the function Graphite alkene feeds intake the 0.1%~10% of quality sum, should polymer containing miscellaneous element or the ionic liquid containing miscellaneous element The quality that feeds intake account for the inner nuclear material, should polymer containing miscellaneous element or ionic liquid, the function fossil containing miscellaneous element Black alkene feeds intake the 1%~20% of quality sum.

For example, preparing the method for negative material provided in an embodiment of the present invention, the quality that feeds intake of the inner nuclear material accounts for Than that can be 85%, the quality accounting that feeds intake of the polymer that should contain miscellaneous element or the ionic liquid containing miscellaneous element can be 5%, then the quality accounting that feeds intake of the functionalization graphene is 10%.

In another example the quality accounting that feeds intake of the inner nuclear material can be 90%, it is somebody's turn to do the polymer containing miscellaneous element or contains The quality accounting that feeds intake of the ionic liquid of miscellaneous element can be 9%, then the quality accounting that feeds intake of the functionalization graphene is 1%.

In another example the quality accounting that feeds intake of the inner nuclear material can be 98.9%, it is somebody's turn to do the polymer containing miscellaneous element or contains The quality accounting that feeds intake of the ionic liquid of miscellaneous element can be 1%, then the quality accounting that feeds intake of the functionalization graphene is 0.1%.

It is to be understood that the inner nuclear material, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, the functionalization The quality accounting that feeds intake of graphene can be other numerical value in above-mentioned numberical range, and the embodiment of the present invention does not limit this specifically It is fixed.

Optionally, as one embodiment, what which carried can be with being coated on the inner nuclear material surface Should the functional group that chemically reacts of polymer containing miscellaneous element or ionic liquid containing miscellaneous element include：Amino-functional Group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro official In energy group, sulfonate functional groups, ester functional groups, itrile group functional group, azo group functional group and siloxy group functional group at least It is a kind of.

Specifically, before sintering, the functionalization graphene need and be coated on inner nuclear material surface this contain The polymer of miscellaneous element or ionic liquid containing miscellaneous element chemically react, and pass through the functional group that functionalization graphene carries It is anti-between the functional group containing miscellaneous element carried with the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element Should, such as by hydrogen bond attraction or condensation reaction, which is fixed on gathering containing miscellaneous element by multiple spot Close on object or ionic liquid containing miscellaneous element, and should polymer containing miscellaneous element or the ionic liquid containing miscellaneous element be It is coated on inner nuclear material surface, therefore the functionalization graphene is also to be evenly coated on inner nuclear material to get outer layer bag It is covered with functionalization graphene, internal layer is coated with the polymer containing miscellaneous element or the kernel material of the ionic liquid containing miscellaneous element Material.Therefore, which is self-contained functional group, which includes：Amido functional group, amidine functional group, Amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro functions, sulfonic group official Can be in group, ester functional groups, itrile group functional group, azo group functional group and siloxy group functional group any one or it is several Combination.

It is to be understood that the method for negative material is prepared provided in an embodiment of the present invention, what which carried Functional group can also be other kinds of functional group, and this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, the polymer containing miscellaneous element being coated on the inner nuclear material surface or contain The functional group that the chemical reaction can occur with the functionalization graphene that the ionic liquid for having miscellaneous element carries includes：Amino-functional Group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro official At least one of energy group, sulfonate functional groups, ester functional groups, itrile group functional group and azo group functional group.

Specifically, doped carbon is by the polymer for containing miscellaneous element or the sintering life of the ionic liquid containing miscellaneous element Into, and graphene is to be sintered to obtain by the functionalization graphene.It is before sintering, it is necessary to the functionalization graphene is equal It is even to be fixed on the inner nuclear material being coated on polymer or ionic liquid containing miscellaneous element, therefore, the function graphite Alkene needs and should contain the polymer of miscellaneous element or the ionic liquid reaction containing miscellaneous element, the i.e. polymerization by containing miscellaneous element Object or the functional group containing the miscellaneous element of ionic liquid carrying containing miscellaneous element and the function of functionalization graphene carrying Reaction between group, such as functionalization graphene fixation is coated on inner nuclear material by hydrogen bond attraction or condensation reaction, Sintering is eventually passed through, is formed and graphene fixation is coated on inner nuclear material surface by doped carbon.The functional group includes：Amino Functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitre In base functional group, sulfonate functional groups, ester functional groups, itrile group functional group and azo group functional group any one or it is several Combination,

It is to be understood that the method for negative material is prepared provided in an embodiment of the present invention, it should polymer containing miscellaneous element Or the functional group that carries of ionic liquid containing miscellaneous element can also be other kinds of functional group, the embodiment of the present invention is herein not It is restricted.

It should also be understood that the miscellaneous element that the polymer for containing miscellaneous element or the ionic liquid containing miscellaneous element contain not only may be used To form the functional group that the polymer for containing miscellaneous element or ionic liquid containing miscellaneous element carry, taken with functionalization graphene The functional group of band is reacted, can preferably by this contain the polymer of miscellaneous element or ionic liquid containing miscellaneous element with should Functionalization graphene is fixed.The presence of the miscellaneous element can also be improved in the negative material prepared by this method The transmission speed of ion, so as to improve the quick charge capability of the battery prepared by the negative material.Miscellaneous element in the doped carbon And provided by the miscellaneous element in the polymer or ionic liquid, what can more be stablized is fixed on inner nuclear material by graphene On.

Optionally, as one embodiment, which includes：Graphite, hard carbon, soft carbon, silicon, silica, silicon-carbon are multiple Close alloy, the above-mentioned metal of object, lithium titanate, silicon alloy, germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, titanium and above-mentioned metal material At least one of mixture of material oxide and above-mentioned material.

Specifically, the method for negative material is prepared provided in an embodiment of the present invention, which can be normal Negative material, for example, it may be graphite, hard carbon, soft carbon, silicon, silica, silicon-carbon compound, lithium titanate, silicon alloy these One or more or metal in compound, such as germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, titanium and these metals Oxide, alloy etc. can also be the one or more in a mixture of these materials.

For example, the inner nuclear material can be graphite, it can also be the mixture of graphite and hard carbon, can also be germanium metal, The either alloy of germanium metal, tin and lead composition, can also be the oxide or alloy of metallic aluminium, can also be that silicon-carbon is compound The mixture of the oxide of object and metallic aluminium composition.

It is to be understood that preparing the method for negative material provided in an embodiment of the present invention, which can also be it The mixture that his material or other materials form, this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, should contain in the polymer of miscellaneous element or the ionic liquid containing miscellaneous element Miscellaneous element includes：At least one of nitrogen, phosphorus, boron, oxygen, sulphur, fluorine, chlorine and protium.

Specifically, since doped carbon is by the polymer for containing miscellaneous element or the warp of the ionic liquid containing miscellaneous element Oversintering obtains, and therefore, should contain should contain miscellaneous element in the polymer of miscellaneous element or the ionic liquid containing miscellaneous element, Also, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element can be carried out preferably instead with functionalization graphene Should, make functionalization graphene more stable and uniform is fixed on the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element On the inner nuclear material of body cladding.For example, the miscellaneous element can be the composition of nitrogen or nitrogen, phosphorus and boron, the present invention is implemented This is not restricted for example.

It is to be understood that the method for negative material is prepared provided in an embodiment of the present invention, it should polymer containing miscellaneous element Or the miscellaneous element in the ionic liquid containing miscellaneous element can also include other miscellaneous elements, the embodiment of the present invention does not limit herein System.

Optionally, as one embodiment, the quality of the miscellaneous element accounts for the polymer for containing miscellaneous element or containing miscellaneous member The 1%~60% of the quality of the ionic liquid of element.

For example, the miscellaneous element is nitrogen, the quality of nitrogen accounts for the polymer containing miscellaneous elemental nitrogen or the ion containing miscellaneous element The 1% of the quality of liquid.

In another example the miscellaneous element is nitrogen, phosphorus and boron, the quality sum of miscellaneous elemental nitrogen, phosphorus and boron, which accounts for, contains these three miscellaneous members The 30% of the polymer containing miscellaneous element of element or the quality of the ionic liquid containing miscellaneous element.

It is to be understood that the quality accounting of the miscellaneous element can be other numerical value in above-mentioned numberical range, the embodiment of the present invention This is not especially limited.

It should also be understood that the quality of miscellaneous element accounts for the 0.1%~30% of the negative material quality being prepared by this method.

Optionally, as one embodiment, should include containing the polymer of miscellaneous element：Sila ring (thiophene is coughed up) polymer, sulphur At least one of heterocycle (thiophene) polymer, organophosphorus polymer, organo-boron polymer and nitrogenous class (pyrroles) polymer.

Specifically, the polymer containing miscellaneous element can select sila ring (thiophene is coughed up) polymer, thia ring (thiophene) poly- At least one of object, organophosphorus polymer, organo-boron polymer and nitrogenous class (pyrroles) polymer are closed, for example, the polymer Can be polyvinylpyrrolidone, melamine resin, Lauxite, melamine resin, polypyrrole, polypyridine, polyphenyl simultaneously Imidazoles, polybenzothiozole, polybenzoxazoles, polyaniline, poly-dopamine, polythiophene, polyphenyl bithiophene, polyphenyl and thiophene are coughed up, poly- phosphorus Any one in acid esters, poly- borate or several compositions.

For example, can should be polypyridine containing the polymer of miscellaneous element, it can also be melamine resin or can also be urea Urea formaldehyde.

In another example it should can also be the mixture of polypyrrole and polypyridine composition containing the polymer of miscellaneous element, either The mixture of sila ring (thiophene is coughed up) polymer and thia ring (thiophene) polymer composition.

It is to be understood that the method for negative material is prepared provided in an embodiment of the present invention, it should polymer containing miscellaneous element It can also include other kinds of polymer, this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, should polymer containing miscellaneous element can be by containing the organic monomer of miscellaneous element It is obtained, should included containing the organic monomer of miscellaneous element by polymerisation：Thiophene coughs up monomer, thiophene monomer, phosphonic acids ester monomer, boric acid At least one of ester monomer and nitrogen containing monomer.

Specifically, in step 110, should can be led to containing the polymer of miscellaneous element by the organic monomer for containing miscellaneous element Polymerisation generation is crossed, i.e., is polymerize on the inner nuclear material surface as polymer by the organic monomer for containing miscellaneous element, obtained The polymer containing miscellaneous element that must be coated on the inner nuclear material surface.The organic monomer for containing miscellaneous element coughs up class including thiophene At least one of monomer, thiophene-based monomer, phosphonic acids ester monomer, boric acid ester monomer and nitrogen heterocycles monomer.It for example, should be containing miscellaneous The organic monomer of element can be pyridine, thiophene, benzimidazole, vinylpyrrolidone, melamine, formaldehyde, pyrroles, bromobenzene Bithiophene, diazosulfide, aniline, diallylamine methylphosphonic acid diethylester and [(2- ethylene oxide methoxyl group) methyl]-phosphine Any one in diethyl phthalate is a variety of.

For example, can should be pyrrole monomer or benzimidazole monomer containing the organic monomer of miscellaneous element.

In another example can should be containing organic monomer of miscellaneous element thiophene and pyridine monomer composition or can be with It is melamine, the composition of three kinds of monomers of formaldehyde and pyrroles.

It is to be understood that the method for negative material is prepared provided in an embodiment of the present invention, organic monomer containing miscellaneous element It can also include other kinds of organic monomer, this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, should include containing the ionic liquid of miscellaneous element：Triphenyl borine, 3- methyl-butvls Pyridine dicyan amine salt, 1- butyl -3- methylimidazole dicyan amine salt, dialkylimidazolium organic sulfonic acid and 1- ethyl-3-methylimidazoles At least one of cdicynanmide.

Specifically, the ionic liquid containing miscellaneous element can select triphenyl borine, 3- methyl-butvl pyridine cdicynanmides In salt, 1- butyl -3- methylimidazole dicyan amine salt, dialkylimidazolium organic sulfonic acid and 1- ethyl-3-methylimidazole cdicynanmides It is at least one.

For example, the ionic liquid that should contain miscellaneous element can be triphenyl borine or can be triphenyl borine 3- methyl-fourth The composition of yl pyridines dicyan amine salt.

It is to be understood that the method for negative material is prepared provided in an embodiment of the present invention, it should ionic liquid containing miscellaneous element Body can also include the other kinds of ionic liquid containing miscellaneous element, and this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, which includes：In doped graphene and graphene oxide extremely Few one kind.

Specifically, the method for negative material is prepared provided in an embodiment of the present invention, graphene is finally by mixing Miscellaneous carbon multiple spot is fixed on inner nuclear material and is evenly coated at inner nuclear material surface, and graphene is burnt by functionalization graphene What knot obtained, which can select at least one of doped graphene and graphene oxide.

For example, the functionalization graphene can select amination graphene in doped graphene, carboxylated graphene, acyl One or any several combination of aminated graphene.

It is to be understood that prepare the method for negative material provided in an embodiment of the present invention, which can be with Other kinds of graphene is selected, this is not restricted for the embodiment of the present invention.

It should also be understood that preparing the method for negative material provided in an embodiment of the present invention, which also may be used To be the functionalization graphene of miscellaneous element of undoping, this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, the doped chemical in the doped graphene includes：Nitrogen, phosphorus, boron, oxygen, sulphur, fluorine, At least one of chlorine and protium.

Specifically, in embodiments of the present invention, the miscellaneous element contained in the doped graphene not only may be constructed this and mix The functional group that miscellaneous graphene carries, the functional group carried with the polymer containing miscellaneous element or ionic liquid is reacted, can be with Preferably the polymer or ionic liquid are fixed with the doped graphene.The presence of the miscellaneous element, can also improve by The transmission speed of negative material intermediate ion prepared by this method, so as to improve the quick charge of the battery prepared by the negative material Ability.

It is to be understood that in the present invention is implemented, the miscellaneous element in the doped graphene can also include other miscellaneous elements, this hair This is not restricted for bright embodiment.

It should also be understood that the order of each step is not meant to the priority of operation order, the execution of each step in the above method The sequencing that order should be subject in actual fabrication process causes any restrictions without tackling the embodiment of the present invention.

The preparation method of negative material provided in an embodiment of the present invention, can when the negative material is as battery cathode Graphene is made to be stably fixed on inner nuclear material, avoids the reunion of graphene, so as to avoid graphene chaotic distribution and Reunite and cause the huge lithium ion battery specific surface area prepared by the negative material, barrier lithium ion transport and and service life The problem of reduction, and this utilizes negative material prepared by this method, has both fast charge and the characteristic of high-energy density, is readily produced And commercialization.

Present invention also provides a kind of negative material, including inner nuclear material and the company being distributed on the inner nuclear material surface Layer and clad are connect, which is connected with the inner nuclear material by the articulamentum, which is to be evenly distributed on the kernel material Expect the graphene of the laminated structure of periphery, which includes doped carbon, a doping carbon particle part and the kernel adhesion, should Another part of doped carbon is connected with the graphene by carbonnitrogen bond.

Specifically, Fig. 1 is the schematic diagram of the structure of the negative material of one embodiment of the invention, as shown in Figure 1, this is negative Pole material includes inner nuclear material and the articulamentum and clad that are distributed on the inner nuclear material surface, the clad are interior with this Nuclear material is connected by the articulamentum, is by chemical anti-between the graphene of the laminated structure of clad and the doped carbon of articulamentum Should be fixed, due to articulamentum be it is fixed be coated on inner nuclear material surface, and pass through chemistry between articulamentum and clad Reaction is fixed, i.e. the graphene of the clad is to be coated on by the doped carbon fixation of articulamentum on the inner nuclear material surface, From the structure of material entirety as can be seen that negative material provided in an embodiment of the present invention structure be equivalent to inner nuclear material this Bead outer cladding the structure of graphene this big ball, the i.e. big ball of similar bead outer cladding, and is to pass through between bead and big ball Doped carbon is fixed, in this way, the relative position of graphene and inner nuclear material will not change, i.e., graphene can be stably fixed to interior On nuclear material surface.

It is to be understood that the structure of negative material shown in FIG. 1 is only a specific embodiment of the invention, the embodiment of the present invention Negative material can be other structures, the embodiment of the present invention be not restricted.For example, the graphene can also be other shapes Shape.

It should also be understood that negative material provided in an embodiment of the present invention can be born by the preparation that the embodiments of the present invention provide The method of pole material is prepared or can also be obtained by other methods, and the embodiment of the present invention be not restricted.

Negative material provided in an embodiment of the present invention is fixed graphene on cladding inner nuclear material surface by doped carbon Negative material can be such that graphene is stably fixed on inner nuclear material surface, the reunion of graphene be avoided, so as to avoid stone The chaotic distribution of black alkene and reunite and cause the specific surface area of the lithium ion battery prepared by the negative material is huge, barrier lithium from The problem of son transmission and service life reduce.Material has both fast charge and the characteristic of high-energy density, and is readily produced and commercial.

Optionally, as one embodiment, which is the polymer containing miscellaneous element or the ion containing miscellaneous element Functional group and the functional group that the clad carries that liquid carries by chemically reacted and heated be carbonized after generate include There is the doped carbon of carbonnitrogen bond.

Specifically, the doped carbon of the articulamentum is by containing the polymer of miscellaneous element or containing miscellaneous element containing miscellaneous element The ionic liquid functional group and the functional group that the clad carries that carry by chemically reacted and heated be carbonized after generate , the functional group and clad that the ionic liquid containing miscellaneous element due to the polymer of miscellaneous element or containing miscellaneous element carries take The element that the functional group of band is contained is carbon and elemental nitrogen, therefore the doped carbon contains carbonnitrogen bond, which is used for doped carbon It is fixedly connected with the graphene.In this way, due to being fixedly connected between graphene and inner nuclear material by articulamentum, it should Graphene just will not generate reunion.

Optionally, as one embodiment, the polymer that should contain miscellaneous element or the ionic liquid containing miscellaneous element pass through Heating melting is coated and fixed in the inner nuclear material periphery, so that by including the carbon nitrogen between the clad and the inner nuclear material The doped carbon of key is fixedly connected.

Specifically, the polymer that should contain miscellaneous element or the ionic liquid containing miscellaneous element are by heating melting cladding On the inner nuclear material surface, and graphene be coated on the inner nuclear material should containing miscellaneous element polymer or contain It is fixed by chemically reacting between the ionic liquid of miscellaneous element, can generates doped carbon after heating is carbonized, that is, pass through doping Carbon will be fixedly connected between the graphene and inner nuclear material.Since articulamentum is that fixation is coated on inner nuclear material surface, and It is fixedly connected between the graphene of clad and the doped carbon of articulamentum by carbonnitrogen bond, therefore, which is fixed It is coated on the inner nuclear material surface, graphene will not generate reunion.

Optionally, as one embodiment, the functional group that the graphene of the clad carries includes：Amido functional group, amine Base functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro functions, At least one of sulfonate functional groups, ester functional groups, itrile group functional group, azo group functional group and siloxy group functional group.

Specifically, the ink alkene need and be coated on inner nuclear material surface should containing miscellaneous element polymer or contain The ionic liquid of miscellaneous element chemically reacts, the functional group and the polymer that are carried by graphene or containing miscellaneous element from Reaction between the functional group containing miscellaneous element that sub- liquid carries, such as by hydrogen bond attraction or condensation reaction, heating Doped carbon can be generated after carbonization, which includes carbonnitrogen bond, and graphene is fixed on polymerization by multiple spot using the carbonnitrogen bond On object or ionic liquid containing miscellaneous element, and should polymer containing miscellaneous element or the ionic liquid containing miscellaneous element be bag It overlays on inner nuclear material surface, therefore the graphene is also to be evenly coated on inner nuclear material to polymer or to contain There is the inner nuclear material of the ionic liquid fixed function graphite alkene cladding of miscellaneous element.Therefore, which is self-contained function The graphene of group, the functional group include：Amido functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxyl official It can group, keto functional group, carbonyl functional group, nitro functions, sulfonate functional groups, ester functional groups, itrile group functional group, azo Any one in base functional group and siloxy group functional group or several combinations.

It is to be understood that in embodiments of the present invention, the functional group which carries can also be other kinds of functional group, This is not restricted for the embodiment of the present invention.

It optionally, should the polymer containing miscellaneous element or the carrying of the ionic liquid containing miscellaneous element as one embodiment Functional group include：Amido functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, ketone group official In energy group, carbonyl functional group, nitro functions, sulfonate functional groups, ester functional groups, itrile group functional group and azo group functional group At least one.

Specifically, in the present invention is implemented, graphene needs to be stably fixed on inner nuclear material, and doped carbon passes through The functional group that the functional group that polymer containing miscellaneous element or the ionic liquid containing miscellaneous element carry carries with clad passes through It is chemically reacted and is obtained after heating carbonization, therefore, which needs and polymer containing miscellaneous element or should contain The ionic liquid reaction of miscellaneous element, i.e., ionic liquid by polymer or containing miscellaneous element carry containing the miscellaneous element Reaction between the functional group that functional group and black alkene carry, such as attracted by hydrogen bond or condensation reaction is by graphene fixed packet It overlays on inner nuclear material, eventually passes through sintering, the polymer that should contain miscellaneous element or the ionic liquid containing miscellaneous element become mixing Miscellaneous carbon forms and graphene fixation is coated on inner nuclear material surface by doped carbon.The functional group includes：Amido functional group, Amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro function Any one in group, sulfonate functional groups, ester functional groups, itrile group functional group and azo group functional group or several groups It closes.

It is to be understood that in embodiments of the present invention, the polymer that should contain miscellaneous element or the ionic liquid containing miscellaneous element are taken The functional group of band can also be other kinds of functional group, and this is not restricted for the embodiment of the present invention.

It should also be understood that the miscellaneous element that the polymer or the ionic liquid containing miscellaneous element contain not only may be constructed the polymerization The functional group that object or ionic liquid containing miscellaneous element carry, the functional group carried with graphene is reacted, can be better The polymer or the ionic liquid containing miscellaneous element are fixed with the graphene.The presence of the miscellaneous element can also improve The transmission speed of the negative material intermediate ion, so as to improve the quick charge capability of the battery prepared by the negative material.This is mixed Miscellaneous element in miscellaneous carbon is also that the miscellaneous element in the ionic liquid by the polymer or containing miscellaneous element provides, and can more be stablized Graphene is fixed on inner nuclear material.

Specifically, in negative material provided in an embodiment of the present invention, inner nuclear material can be common negative material, It is for example, it may be a kind of in graphite, hard carbon, soft carbon, silicon, silica, silicon-carbon compound, lithium titanate, silicon alloy these compounds Or a variety of or metal, such as germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, oxide, the alloy of titanium and these metals Deng can also be the one or more in a mixture of these materials.

It is to be understood that in negative material provided in an embodiment of the present invention, the inner nuclear material can also be other materials or The mixture of other materials composition, this is not restricted for the embodiment of the present invention.

Specifically, since doped carbon is that the ionic liquid by the polymer or containing miscellaneous element is obtained through oversintering, Therefore, miscellaneous element, also, the polymerization containing miscellaneous element should be contained in the polymer or the ionic liquid containing miscellaneous element Object and ionic liquid containing miscellaneous element can preferably be reacted with functionalization graphene, make functionalization graphene more steady It is fixed to be uniformly fixed on the inner nuclear material of polymer or the ionic liquid cladding containing miscellaneous element.For example, the miscellaneous element can To be the composition of nitrogen or nitrogen, phosphorus and boron, this is not restricted for the embodiment of the present invention.

It is to be understood that in embodiments of the present invention, the miscellaneous element in the polymer or ionic liquid containing miscellaneous element may be used also To include other miscellaneous elements, this is not restricted for the embodiment of the present invention.

For example, the miscellaneous element is nitrogen, the quality of nitrogen accounts for the polymer containing miscellaneous elemental nitrogen or the ion containing miscellaneous element The 20% of the quality of liquid.

In another example the miscellaneous element is nitrogen, phosphorus and boron, the quality sum of miscellaneous elemental nitrogen, phosphorus and boron, which accounts for, contains these three miscellaneous members The 60% of the quality of the polymer of element or the ionic liquid containing miscellaneous element.

It should also be understood that the quality of miscellaneous element accounts for the 0.1%~30% of the negative material quality.

It is to be understood that in embodiments of the present invention, it should can also include other kinds of polymerization containing the polymer of miscellaneous element Object, this is not restricted for the embodiment of the present invention.

Specifically, should can be given birth to containing the polymer of miscellaneous element by the organic monomer for containing miscellaneous element by polymerisation Into, i.e., polymerize by the organic monomer for containing miscellaneous element on the inner nuclear material surface, formation be coated on inner nuclear material surface The polymer containing miscellaneous element.The organic monomer for containing miscellaneous element coughs up class monomer, thiophene-based monomer, phosphonate ester list including thiophene At least one of body, boric acid ester monomer and nitrogen heterocycles monomer.For example, can should be pyrrole containing the organic monomer of miscellaneous element Pyridine, thiophene, benzimidazole, vinylpyrrolidone, melamine, formaldehyde, pyrroles, bromo benzothiophene, diazosulfide, benzene Any one in amine, diallylamine methylphosphonic acid diethylester and [(2- ethylene oxide methoxyl group) methyl]-diethyl phosphonate or Person is a variety of.

It is to be understood that in embodiments of the present invention, the organic monomer containing miscellaneous element can also include other kinds of organic Monomer, this is not restricted for the embodiment of the present invention.

It is to be understood that in embodiments of the present invention, the ionic liquid that should contain miscellaneous element can also include other kinds of contain There is the ionic liquid of miscellaneous element, this is not restricted for the embodiment of the present invention.

Optionally, as one embodiment, which includes：At least one in doped graphene and graphene oxide Kind.

Specifically, in embodiments of the present invention, graphene is finally to be fixed on by doped carbon multiple spot on inner nuclear material And inner nuclear material surface is evenly coated at, which can select at least one of doped graphene and graphene oxide

For example, the graphene can select amination graphene in doped graphene, carboxylated graphene, amide groups One or any several combination in graphene or graphene oxide.

It is to be understood that in negative material provided in an embodiment of the present invention, which can also select other kinds of stone Black alkene, this is not restricted for the embodiment of the present invention.

Specifically, in embodiments of the present invention, the miscellaneous element contained in the doped graphene not only may be constructed this and mix The functional group that miscellaneous graphene carries, with the functional group that the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element carry into Preferably the polymer or ionic liquid containing miscellaneous element can be fixed with the doped graphene for row reaction.This is miscellaneous The presence of element can also improve the transmission speed of the negative material intermediate ion, so as to improve the electricity prepared by the negative material The quick charge capability in pond.

The embodiment of the present invention additionally provides a kind of cathode pole piece, which includes collector and coated in the collector On the embodiments of the present invention provide negative material.

Specifically, by negative material provided in an embodiment of the present invention, (doped carbon fixes graphene coated inner nuclear material Negative material) mixed with conductive agent, binding agent and solvent, coating on a current collector, for example, the collector can be aluminium foil or Then copper foil is dried, roll-in, and punching obtains the cathode pole piece.

Cathode pole piece provided in an embodiment of the present invention can make the graphene in negative material be stably fixed to kernel material On material, the reunion of graphene is avoided, lithium ion transport can be obstructed and make by solving the lithium ion battery prepared by the cathode pole piece The problem of with service life reduction.

The embodiment of the present invention additionally provides a kind of lithium ion battery, the lithium ion battery include cathode pole piece, anode pole piece, Membrane, nonaqueous electrolytic solution and shell, wherein, which includes collector and coated in above-mentioned hair on the collector The negative material that bright embodiment provides.

Lithium ion battery provided in an embodiment of the present invention can be such that graphene is stably fixed on inner nuclear material, avoid The reunion of graphene, so as to avoid graphene chaotic distribution and reunite and cause battery specific surface area is huge, barrier lithium from The problem of son transmission and service life reduce, improves the charge rate and service life of the lithium ion battery, and is readily produced And commercialization.

With reference to specific embodiment, preparation method to the negative material of the embodiment of the present invention and contain the cathode material The preparation method of the lithium battery of material is described in detail.

Embodiment one, using graphite as inner nuclear material, functionalization graphene selects amination graphene, poly- containing miscellaneous element It closes exemplified by object selects polypyrrole and illustrates, be as follows：

Step 201, the preparation of amination graphene：At room temperature, the mixed liquor of the sulfuric acid of 360ml and the phosphoric acid of 40ml is taken, It is slowly added into mixed liquor in 10g native graphites, then adds in 18g potassium permanganate in mixture, control adds in speed, makes Reaction temperature is controlled between 35~40 DEG C, after the completion of addition, when stirring 12 is small when system is warming up to 50 DEG C, treats reaction system After being cooled to room temperature, the 400ml ice water of the 30w% hydrogenperoxide steam generators dissolved with 3ml is imported into reaction solution, by mixed liquor mistake Filter, filter residue and is diluted to pH=7 by the salt acid elution of 30w% with distilled water, by obtained filter residue in vacuum drying oven, control When temperature is that 40 DEG C of dryings 24 are small, graphene oxide is obtained.10g graphene oxides is taken to add in ultrasonic vibration in 40ml ethylene glycol, Then add in 1ml ammonium hydroxide, obtain the mixing liquid of brownish black, by the mixing liquid be heated to 180 DEG C reaction 10 it is small when, then drop Temperature filtering, filter cake are washed with distilled water, and by the filter cake after washing in vacuum drying oven, when set temperature is that 60 DEG C of dryings 24 are small, are obtained To amination graphene.

Step 202, polypyrrole fixes the preparation of amination graphene coated graphite：By cetyl trimethylammonium bromide (hexadecyltrimethy ammonium bromide, CTAB, (C16H33) N (CH3) 3Br) 730g is dissolved in ice-water bath Concentration is in 12L hydrogen chloride (HCl) solution of 1mol/L, adds 1kg native graphites, then ultrasonic disperse 30 minutes adds in 1370g ammonium persulfates (ammonium persulphate, APS) form the suspension of white, and suspension stirring 0.5 is small Shi Hou adds 500mL pyrrole monomers (Pyrrole), and set temperature is that insulation reaction filters afterwards for 24 hours at 4 DEG C in incubator, Obtained black precipitate is washed three times with the HCl solution of 1mol/L, then with pure water washing to solution in colourless neutrality, so Sediment is dried for 24 hours at 80 DEG C afterwards.Obtain polypyrrole coated graphite.Obtained polypyrrole coated graphite is placed in cladding kettle In, by polypyrrole coated graphite：The mass ratio of amination graphene is 100:10 ratio adds in amino graphite, will coat kettle 200 DEG C are warming up to, when high-speed stirred 4 is small, cools down out kettle, polypyrrole is obtained and fixes amination graphene coated graphite.

Step 203, doped carbon fixes the preparation of the negative material of graphene coated graphite：Polypyrrole is fixed into amino fossil Black alkene coated graphite is placed in atmosphere sintering furnace, is passed through nitrogen, 800 DEG C is warming up to 5 DEG C/min heating rates, then 800 DEG C heat preservation 2 it is small when, cool to room temperature, discharge, obtain doped carbon fix graphene coated graphite negative material.

Step 204, the preparation of the lithium battery of the negative material of graphene coated graphite is fixed comprising doped carbon：Take doped carbon Fixed graphene coated graphite, conductive black, polyvinylidene fluoride are using mass ratio as 85：10：5 ratio is in N- crassitudes It is uniformly mixed in ketone, and the mixture is uniformly applied in copper foil current collector, the vacuum drying at 120 DEG C, roll-in obtains cathode Pole piece.Anode pole piece takes cobalt acid lithium, other are the same as cathode pole piece preparation method.Positive and negative anodes membrane is taken to be prepared into according to winding process Soft package lithium battery.

Embodiment two, using graphite as inner nuclear material, functionalization graphene select amination graphene, containing miscellaneous element from Sub- liquid illustrates exemplified by selecting triphenyl borine acid esters, is as follows：

Step 301, doped carbon fixes the preparation of the negative material of graphene coated graphite：Under dry atmosphere, by 500g Triphenyl borine acid esters is placed in 2kg expanded graphites in cladding kettle, under the conditions of inert gas shielding, is stirred in the case where temperature is 200 DEG C 3h, uniformly after mixing, by graphite：The mass ratio of amination graphene is 100:10 ratio adds in amination graphene, maintains The temperature of kettle is coated as 200 DEG C, when stirring 3 is small, cools down out kettle.It obtains triphenyl borine acid esters and fixes amination graphene cladding stone Ink, will obtain triphenyl borine acid esters fix amination graphene coated graphite be placed in atmosphere sintering furnace, be passed through nitrogen, with 5 DEG C/ Min heating rates are warming up to 800 DEG C, then when 800 DEG C of heat preservations 2 are small, cool to room temperature, discharge, obtain doped carbon anchor stone The negative material of black alkene coated graphite.

Step 302, the preparation of the lithium battery of the negative material of graphene coated graphite is fixed comprising doped carbon：Take doped carbon Fixed graphene coated graphite, conductive black, polyvinylidene fluoride are using mass ratio as 85：10：5 ratio is in N- crassitudes It is uniformly mixed in ketone, and the mixture is uniformly applied in copper foil current collector, the vacuum drying at 120 DEG C, roll-in obtains cathode Pole piece.Anode pole piece takes cobalt acid lithium, other are the same as cathode pole piece preparation method.Positive and negative anodes membrane is taken to be prepared into according to winding process Soft package lithium battery.

Embodiment three, using graphite as inner nuclear material, functionalization graphene selects amide groups graphite alkene or amido fossil Black alkene, the polymer containing miscellaneous element are illustrated exemplified by selecting melamine resin, are as follows：

Step 401, the preparation of amide groups graphite alkene：At room temperature, the mixing of the sulfuric acid of 360ml and the phosphoric acid of 40ml is taken Liquid is slowly added to 10g native graphites into mixed liquor, and 18g potassium permanganate then is added in mixture, and control adds in speed, makes Reaction temperature is controlled between 35~40 DEG C, after the completion of addition, when stirring 12 is small when system is warming up to 50 DEG C, treats reaction system After being cooled to room temperature, the 400ml ice water of the 30w% hydrogenperoxide steam generators dissolved with 3ml is imported into reaction solution, by mixed liquor mistake Filter, filter residue and is diluted to PH=7 by the salt acid elution of 30w% with distilled water, by obtained filter residue in vacuum drying oven, control When temperature is that 40 DEG C of dryings 24 are small, graphene oxide is obtained.10g graphene oxides are taken, ultrasonic vibration is dispersed in the diformazan of 100ml In base formamide (dimethyl formamide, DMF), keep temperature for 30 DEG C and stir 1 it is small when, then add in 300ml 1, 6- diamines or ethylenediamine and stir 1 it is small when, then into mixed liquor add in 10mg coupling agents 2- (three nitrogen of 7- azos benzo Azoles)-N, N, N', N'- tetramethylurea hexafluorophosphoric acids ester (2- (7-Aza-1H-benzotriazole-1-yl) -1,1,3,3- Tetramethyluronium hexafluorophosphate, HATU) stir evenly after, reaction solution is transferred to 60 DEG C of water-baths In, 6h is stirred at reflux, stops reaction after reaction solution cools to room temperature, reaction solution is imported in 1.6L ethyl alcohol, filtering, and use second Excessive diamines is removed in alcohol washing, and filter residue is placed in vacuum drying oven, and set temperature for 24 hours, obtains amide groups for 50 DEG C of dryings Graphene.

Step 402, melamine resin fixes the preparation of amide groups graphite alkene coated graphite：By 1kg graphite and 40g melamine trees Fat or 1kg graphite and 20g melamine resins are placed in cladding kettle, under the conditions of inert gas shielding, are stirred at a temperature of 100 DEG C Coat 3 it is small when, cooling.Then cladding kettle is opened, it is corresponding to add in 50g acyls for being initially added 1kg graphite and 40g melamine resins Aminated graphene, alternatively, for being initially added 1kg graphite and 20g melamine resins, it is corresponding to add in the aminated graphenes of 50g, Under inert gas atmosphere protective condition, cladding kettle is warming up to 200 DEG C, when stirring 3 is small, cools down out kettle, discharging obtains melamine tree Fat fixes amide groups graphite alkene coated graphite.

Step 403, doped carbon fixes the preparation of the negative material of graphene coated graphite：Melamine resin is fixed into amide groups Graphite alkene coated graphite is placed in atmosphere sintering furnace, is passed through nitrogen, is warming up to 800 DEG C with 5 DEG C/min heating rates, Ran Hou When 800 DEG C of heat preservations 2 are small, room temperature is cooled to, is discharged, obtains the negative material that doped carbon fixes graphene coated graphite.

Step 404, the preparation of the lithium battery of the negative material of graphene coated graphite is fixed comprising doped carbon：Take doped carbon Fixed graphene coated graphite, conductive black, polyvinylidene fluoride are using mass ratio as 85：10：5 ratio is in N- crassitudes It is uniformly mixed in ketone, and the mixture is uniformly applied in copper foil current collector, the vacuum drying at 120 DEG C, roll-in obtains cathode Pole piece.Anode pole piece takes cobalt acid lithium, other are the same as cathode pole piece preparation method.Positive and negative anodes membrane is taken to be prepared into according to winding process Soft package lithium battery.

Example IV, using graphite as inner nuclear material, functionalization graphene selects graphene oxide or carboxylated graphene, Polymer containing miscellaneous element illustrates exemplified by selecting Lauxite, is as follows：

Step 501, the preparation of Lauxite fixed function graphite alkene coated graphite：By 1kg graphite and 20g Lauxites It is placed in cladding kettle, under the conditions of inert gas shielding, when stirring cladding 3 is small at a temperature of 100 DEG C, cooling.Then cladding is opened Kettle, adds in 50g graphene oxides or 50g carboxylated graphenes, and under inert gas atmosphere protective condition, cladding kettle is warming up to 200 DEG C, when stirring 3 is small, kettle is cooled down out, discharging obtains Lauxite fixed function graphite alkene coated graphite.

Step 502, doped carbon fixes the preparation of the negative material of graphene coated graphite：By Lauxite fixed function Graphene coated graphite is placed in atmosphere sintering furnace, is passed through nitrogen, is warming up to 800 DEG C with 5 DEG C/min heating rates, Ran Hou When 800 DEG C of heat preservations 2 are small, room temperature is cooled to, is discharged, obtains the negative material that doped carbon fixes graphene coated graphite.

Step 503, the preparation of the lithium battery of the negative material of graphene coated graphite is fixed comprising doped carbon：Take doped carbon Fixed graphene coated graphite, conductive black, polyvinylidene fluoride are using mass ratio as 85：10：5 ratio is in N- crassitudes It is uniformly mixed in ketone, and the mixture is uniformly applied in copper foil current collector, the vacuum drying at 120 DEG C, roll-in obtains cathode Pole piece.Anode pole piece takes cobalt acid lithium, other are the same as cathode pole piece preparation method.Positive and negative anodes membrane is taken to be prepared into according to winding process Soft package lithium battery.

In order to further illustrate the negative material of the embodiment of the present invention, graphene coated is fixed by the polymer to preparation Graphite material (un-sintered, the generation of non-impurity-doped carbon), doped carbon coated graphite material (not adding graphene), the carbon-coated stone of doping Black admixed graphite alkene material (first generating doped carbon, add graphene), doped carbon fix microcosmic group of graphene covering material The comparison of structure is knitted to illustrate that doped carbon provided in an embodiment of the present invention fixes graphene covering material performance.

Fig. 2 is stereoscan photograph (the scanning electron that polymer fixes graphene coated graphite material Microscope, SEM), Fig. 3 is the SEM photograph that doped carbon fixes graphene coated graphite material, it can be seen that shown in Fig. 2 The polymer position that polymer is fixed on the outside of graphene coated graphite material graphene is relative smooth.It can from Fig. 3 To find out, after the sintering, polymer generation doped carbon becomes a little little particles and is fixed on graphene, and graphene is close solid It is scheduled on graphite, after sintering, the polymer between graphene and graphite does not occur.

Fig. 4 is transmission electron microscope (the Transmission electron that doped carbon fixes graphene coated graphite material Microscope, TEM) photo, as can be seen from Figure 4 between graphene with the presence of little particle, infer graphene and graphite it Between also have short grained presence.

Fig. 5 is the SEM photograph for the doped carbon coated graphite material for being not added with graphene, and Fig. 6 is to add mixing after graphene The SEM photograph of miscellaneous carbon fixation graphene coated graphite material, from figure 5 it can be seen that being not added with the doping carbon coating of graphene Graphite material graphite surface is smooth.From fig. 6 it can be seen that the doped carbon after addition graphene fixes the graphite of graphene coated There is more protrusion on surface.Fig. 5 is consistent with the polymer ingredient proportion of two kinds of materials shown in Fig. 6, and processing mode is also Consistent, the doping carbon amounts retained is also consistent.It is SEM ranks because size is smaller, doped carbon can not embody.Cause The more protrusion seen in this Fig. 6 is graphene.

Fig. 7 is the SEM photograph of doped carbon coated graphite admixed graphite alkene material, and Fig. 8 is that doped carbon fixes graphene coated The TEM photos of graphite material it can be seen from figure 7 that being to tilt without the fixed graphene of doped carbon, can not be stablized and deposit On graphite.As can be seen from Figure 8, doped carbon fixes the protrusion of the graphite surface of graphene coated as graphene film, and Uniform coated graphite material.

In order to further illustrate the performance of battery prepared by negative material according to embodiments of the present invention, by doped carbon Soft-package battery, the dry-mixed graphene of doped carbon coated graphite prepared by fixed graphene coated graphite negative material (first is adulterated by generation Carbon adds graphene) soft-package battery prepared by negative material and do not contain Soft Roll prepared by graphene negative material The performance of battery is compared.

The first effect that the full battery A of the obtained Soft Roll of graphene coated graphite negative material is fixed by doped carbon is 89%, Capacity is 517.8mah, the first effect 84% compared with the soft-package battery B prepared by the dry-mixed graphene negative material of doped carbon coated graphite, Capacity is high for 499mah, the soft-package battery containing graphene, does not all contain the Soft Roll electricity prepared by graphene negative material relatively The capacity of pond C is high, and battery C capacity is 450mah, and head effects are 88%.Test the big multiplying power charging performance of battery.It is carrying out first Constant current 3.5A electric currents are directly filled under rear constant pressure 4.2V charge conditions, and the constant current of battery A directly fills the time for 4.2min, is filled with electricity 50%, the time is directly filled for 3.5min compared with battery B constant currents, and the rapid charging performance for being filled with electricity 40% is superior.It charges in big multiplying power 5C In the cyclic process of 0.7C electric discharges, the capacity retention ratio of 200 weeks Xun Huans of battery A is 90%, the appearance of 200 weeks Xun Huans of battery B Amount conservation rate only has 80%.Since loose graphene is easily reunited, during charge and discharge cycles, used as additive Graphene loses capacity because of reuniting, by with polymer reaction and fixed graphene then because be well fixed on graphite On, capacitance loss is slower.The 3.5A electric currents of battery C directly fill the time and there was only 1min, and 5C charge and discharge cycles also decay rapidly.Doped carbon Soft-package battery prepared by the negative material of fixed graphene coated graphite has the first effect of preferable capacity and cycle life characteristics.

It is to be understood that in various embodiments of the present invention, the size of the sequence number of above-mentioned each process is not meant to perform suitable The priority of sequence, depending on the execution sequence of each process should be with the order in its actual step, the reality without tackling the embodiment of the present invention It applies process and forms any restriction.

It should also be understood that term "and/or" in the embodiment of the present invention, is only a kind of incidence relation for describing affiliated partner, Expression may have three kinds of relations.Specifically, A and/or B can be represented：Individualism A exists simultaneously A and B, individualism B These three situations.In addition, character "/" herein, it is a kind of relation of "or" to typically represent forward-backward correlation object.

The above is only the specific embodiment of the embodiment of the present invention, but the protection domain of the embodiment of the present invention is not This is confined to, in the technical scope that any one skilled in the art discloses in the embodiment of the present invention, can be thought easily To change or replacement, should all cover within the protection domain of the embodiment of the present invention.Therefore, the protection domain of the embodiment of the present invention It should be subject to the protection scope in claims.

Claims

A kind of 1. method for preparing negative material, which is characterized in that including：

Inner nuclear material and the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element are mixed and heated, so that described contain There are the polymer of miscellaneous element or the ionic liquid containing miscellaneous element to coat the inner nuclear material；

The polymer containing miscellaneous element or the inner nuclear material of the ionic liquid containing miscellaneous element and function fossil are coated with by described Black alkene is mixed and heated so that the functionalization graphene cladding polymer containing miscellaneous element or containing miscellaneous element from Sub- liquid and the inner nuclear material；

By the functionalization graphene, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element and it is described in Nuclear material is sintered, and obtains the cathode that graphene fixation is coated on to the inner nuclear material surface by doped carbon Material.
2. according to the method described in claim 1, it is characterized in that, the polymer containing miscellaneous element can be by containing miscellaneous member Element organic monomer obtained by polymerisation, it is described by inner nuclear material with containing miscellaneous element mixed with polymers and heating, with The polymer containing miscellaneous element or the ionic liquid containing miscellaneous element is made to coat the inner nuclear material, including：

The inner nuclear material and the organic monomer containing miscellaneous element are mixed and heated, pass through the having containing miscellaneous element The polymerisation generation polymer that contains miscellaneous element of the machine monomer on the inner nuclear material surface, so that described containing miscellaneous Inner nuclear material described in the polymer overmold of element.
3. method according to claim 1 or 2, which is characterized in that the functionalization graphene contains miscellaneous element with described Polymer or the ionic liquid containing miscellaneous element between be the functional group and institute carried by the functionalization graphene The chemical reaction stated between the functional group of the polymerization containing miscellaneous element or the ionic liquid carrying containing miscellaneous element is fixed.
4. according to the method in any one of claims 1 to 3, which is characterized in that the quality that feeds intake of the inner nuclear material accounts for The inner nuclear material, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, the function graphite Alkene feeds intake the 79.9%~98.9% of quality sum, and the quality that feeds intake of the functionalization graphene accounts for the inner nuclear material, described Polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, the functionalization graphene feed intake quality sum 0.1%~10%, the quality that feeds intake of the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element accounts for described Inner nuclear material, the polymer containing miscellaneous element or the ionic liquid containing miscellaneous element, the functionalization graphene are thrown Expect the 1%~20% of quality sum.
5. the method according to claim 3 or 4, which is characterized in that the functional group that the functionalization graphene carries includes： Amido functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl function Group, nitro functions, sulfonate functional groups, ester functional groups, itrile group functional group, azo group functional group and siloxy group functional group At least one of.
6. method according to any one of claim 3 to 5, which is characterized in that the polymer containing miscellaneous element or The functional group that the ionic liquid containing miscellaneous element carries includes：Amido functional group, amidine functional group, amido functionality, Carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro functions, sulfonate functional groups, ester group function At least one of group, itrile group functional group and azo group functional group.
7. method according to any one of claim 1 to 6, which is characterized in that the inner nuclear material includes：It is graphite, hard Carbon, soft carbon, silicon, silica, silicon-carbon compound, lithium titanate, silicon alloy, germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, titanium and above-mentioned At least one of mixture of the alloy of metal material, above-mentioned metal material oxide and above-mentioned material.
8. method according to any one of claim 1 to 7, which is characterized in that it is characterized in that, described contain miscellaneous element Polymer include：Sila ring (thiophene is coughed up) polymer, thia ring (thiophene) polymer, organophosphorus polymer, organo-boron polymer At least one of with nitrogenous (pyrroles) polymer.
9. according to the method described in claim 8, it is characterized in that, the quality of the miscellaneous element accounts for the gathering containing miscellaneous element Close the 1%~60% of the quality of object.
10. a kind of negative material, which is characterized in that including inner nuclear material and the connection being distributed on the inner nuclear material surface Layer and clad, the clad are connected with the inner nuclear material by the articulamentum, and the clad is is evenly distributed on The graphene of the laminated structure of inner nuclear material periphery is stated, the articulamentum includes doped carbon, a part for the doped carbon and institute Kernel adhesion is stated, another part of the doped carbon is connected with the graphene by carbonnitrogen bond.
11. negative material according to claim 10, which is characterized in that the articulamentum is the polymer containing miscellaneous element Or the functional group that the functional group of the ionic liquid carrying containing miscellaneous element carries with the clad is by being chemically reacted simultaneously The doped carbon for including the carbonnitrogen bond generated after heating carbonization.
12. negative material according to claim 11, which is characterized in that the polymer containing miscellaneous element or containing miscellaneous The ionic liquid of element is coated and fixed by heating melting in the inner nuclear material periphery, so that the clad and the kernel It is fixedly connected between material by including the doped carbon of the carbonnitrogen bond.
13. the negative material according to claim 11 or 12, which is characterized in that functional group's bag that the clad carries It includes：Amido functional group, amidine functional group, amido functionality, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl official It can group, nitro functions, sulfonate functional groups, ester functional groups, itrile group functional group, azo group functional group and siloxy group function At least one of group.
14. the negative material according to any one of claim 11 to 13, which is characterized in that described poly- containing miscellaneous element Closing the functional group that object or the ionic liquid containing miscellaneous element carry includes：Amido functional group, amidine functional group, amide groups function Group, carboxyl functional group, hydroxy functional group, keto functional group, carbonyl functional group, nitro functions, sulfonate functional groups, ester group official At least one of energy group, itrile group functional group and azo group functional group.
15. the negative material according to any one of claim 10 to 14, which is characterized in that the inner nuclear material includes： Graphite, hard carbon, soft carbon, silicon, silica, silicon-carbon compound, lithium titanate, silicon alloy, germanium, tin, lead, antimony, bismuth, zinc, aluminium, iron, titanium And at least one of mixture of the alloy of above-mentioned metal material, above-mentioned metal material oxide and above-mentioned material.
16. the negative material according to any one of claim 11 to 15, which is characterized in that described poly- containing miscellaneous element Closing object includes：Sila ring (thiophene is coughed up) polymer, thia ring (thiophene) polymer, organophosphorus polymer, organo-boron polymer and contain At least one of nitrogen (pyrroles) polymer.
17. negative material according to claim 16, which is characterized in that the quality of the miscellaneous element, which accounts for, described contains miscellaneous member The 1%~60% of the quality of the polymer of element.
18. a kind of cathode pole piece, which is characterized in that the cathode pole piece includes collector and coated in the power on the collector Profit requires the negative material any one of 10 to 17.
19. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes cathode pole piece, anode pole piece, membrane, non- Water electrolysis liquid and shell, wherein, the cathode pole piece includes collector and coated in the claim 10 on the collector To the negative material any one of 17.