CN104638242A - Method for synthesizing lithium ion battery cathode material lithium iron phosphate through in situ polymerizing and cladding - Google Patents
Method for synthesizing lithium ion battery cathode material lithium iron phosphate through in situ polymerizing and cladding Download PDFInfo
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- CN104638242A CN104638242A CN201510063406.9A CN201510063406A CN104638242A CN 104638242 A CN104638242 A CN 104638242A CN 201510063406 A CN201510063406 A CN 201510063406A CN 104638242 A CN104638242 A CN 104638242A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a method for synthesizing lithium ion battery cathode material lithium iron phosphate through in situ polymerizing and cladding. The lithium iron phosphate is prepared by the following steps of (1) dissolving a phosphorus source in water and uniformly mixing, and then adding a polymer monomer into the mixed liquor under stirring and uniformly mixing, wherein the polymer monomer is one of phenylamine, pyrrole, crylic acid, vinyl cyanide, ethylene glycol, vinyl chloride and vinyl benzene; (2) slowly adding an iron source solution into the mixed solution prepared in the step (1), and mixing the two solutions to react so as to prepare a precursor solution; (3) adding a lithium source into the precursor solution, stirring intensely, and performing spray drying to prepare precursor powder; and (4) calcining the precursor powder at high temperature to prepare a nanoscale porous LiFePO4/C sample. The material prepared by the method is relatively high in charge and discharge capacity, relatively good in rate capability and excellent in cycling performance. The lithium iron phosphate is synthesized by a solid-liquid combination method easy to be commercialized, the method is easy to operate and short in technological process; besides substituted sources are easily available, and the manufacturing cost is low.
Description
Technical field
The present invention relates to the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of a kind of in-situ polymerization.
Background technology
The anode material of lithium battery of commercial small size battery mainly cobalt acid lithium in the market, but cobalt acid lithium is due to its crystal structure and thermally-stabilised difference, and there is larger safety risks problem, and cobalt resource is limited, cost is higher, can only be applied in compact battery at present.In Large Copacity high power battery field, phosphoric acid based material, manganese based material, nickel-cobalt-manganese ternary based material are the main positive electrodes of application at present.Because nickel, the cobalt prices of raw and semifnished materials go up always, although so ternary material fail safe improves to some extent, cost is difficult to lower; LiMn2O4 is due to its congenital fault of construction, and cycle performance is bad, so in use cost, even high than lead-acid battery.And LiFePO
4after completely de-lithium, a axle and b axle shrink 5% and 3.6% respectively, and c-axis direction extends 2%, and whole unit cell volume reduces about 6.5%, and density of material increases by 2.6%; Change in charging process between Fe-O key is very little, can not more than 2.8nm.I.e. LiFePO in whole charge and discharge process
4the change of crystal volume is very little, and therefore, it has good fail safe and cycle performance as anode material for lithium-ion batteries.Work as LiFePO
4when forming battery with Carbon anode, this less volume contraction just in time makes up the expansion of Carbon anode, thus can reduce internal stress largely, and this is significant to the volume utilization improving lithium ion battery.Therefore, the improvement of the preparation and property of LiFePO4 is of great importance.
The preferred material that LiFePO4 is applied as great-capacity power battery gets most of the attention, but the intrinsic two large shortcomings of LiFePO4 seriously hinder its further large-scale promotion again in all trades and professions.Main cause has 2 points: one is due to Li
+at LiFePO
4after deviating from, the FePO of generation
4there are orthorhombic and the brilliant two kinds of crystal structures of triangle, and the FePO of triangle crystal formation
4be non-electroactive, cause the electronic conductivity of material poor---pure phase LiFePO
4electronic conductivity σ
eabout 10
-9s/cm magnitude, and usually used as the electronic conductivity σ of lithium rechargeable battery material
eshould 10 be not less than
-3s/cm magnitude; Its two due on electrolyte and electrolyte/electrode material interface by Li
+diffusion mobility carrys out conduct charges, therefore LiFePO
4ionic conductivity by Li
+diffusive migration determines.PO between octahedron
4tetrahedron limits the change of cell volume, limits Li
+movement, Li
+can only carry out embedding and deviating from along the axial passage of b, therefore LiFePO
4one dimension Li can only be had
+transmission channel, relative Li
2mn
2o
4three-dimensional transmission channel LiFePO
4li
+diffusive migration speed is much smaller, therefore LiFePO
4ionic conductivity σ
e10
-11s/cm magnitude.If LiFePO
4crystallization imperfect, high preferred orientation is declined, then Li
+diffusive migration passage is more easily obstructed, LiFePO
4the ionic conductivity of material can reduce further, and this is to LiFePO
4the raising of high rate capability is very unfavorable.
For improving LiFePO4 electronic conductivity and the low two large problems of lithium ion diffusion rate, the measure taked at present is mainly adulterated, coated and preparation nanometer materials.But adopt metal ion mixing (magnesium, aluminium, zirconium etc.), the crystal structure of material changes, and the metal ion adulterated may occupy lithium position, affects the performance of material comprehensive electrochemical properties simultaneously.Coated or preparation nano material is adopted to be effective method improving the large shortcoming of LiFePO4 two of generally acknowledging at present.If but be that the nano particle of nonactive coating layer or preparation is uneven to LiFePO4 coated, electronic conductivity or the lithium ion diffusion rate of so prepared material can not get effective improvement, and affect the electrical property of material.As:
CN1280185C discloses a kind of preparation method of lithium iron phosphate positive material, and the polymer that the method apparatus is conductive or macromolecular compound carry out coated to LiFePO4, comprehensively improves specific capacity and the cycle performance of material.
CN101728518B discloses a kind of method preparing lithium iron phosphate positive material, and the method, by adding acetylene black in raw material building-up process, improves the discharge capacity of material.
CN101728519B discloses the synthetic method of the coated anode material of lithium battery of a kind of sucrose.The method improves the cycle performance of material to a certain extent, but the first discharge specific capacity of material is lower.
CN101567449B disclose a kind of by conductive doped ion and supercharging ion synthesis nano lithium electricity positive electrode preparation method.Material electric conductivity prepared by the method and voltage platform are improved, but the cycle performance of material is not good enough.
Summary of the invention
For existing problem, the object of the present invention is to provide a kind of method of in-stiu coating synthesizing lithium ionic cell positive pole material lithium iron phosphate.
To achieve these goals, technical scheme of the present invention is such: the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of a kind of in-situ polymerization, is characterized in that: be prepared as follows:
(1), by phosphorus source be dissolved in water and mix, under agitation joined by polymer monomer in above-mentioned solution, described polymer monomer is the one in aniline, pyrroles, acrylic acid, acrylonitrile, ethylene glycol, vinyl chloride, styrene;
(2) slowly add, again by source of iron solution in the mixed solution in step (1), be obtained by reacting precursor solution;
(3), by lithium source add in above-mentioned precursor solution, vigorous stirring, then spraying dry obtains precursor powder;
(4), above-mentioned precursor powder is obtained LiFePO through high-temperature calcination
4/ C.
Adopt such scheme, after polymer monomer is uniformly dispersed in microcosmic salt solution, ferric salt solution is slowly added wherein.The principle reacted in the process is as follows:
Fe
3++PO
4 3-→FePO
4(a)
n(M)→PM (b)
Wherein in b reaction equation, M is polymer monomer, and PM is polymer.First there is the reaction of (a) formula when trivalent iron salt adds in solution and generate FePO
4, meanwhile monomer M is at Fe
3+initiation under polymerization generate polymer P M, the coated FePO of final polymer P M
4particle forms FePO
4/ PM compound.The present invention completes monomer polymerization while source of iron and phosphorus source Reactive Synthesis ferric phosphate, at formation FePO
4coated PM while precipitation, be that original position activity is coated, PM limits FePO
4growing up further of particle, obtains nanoscale FePO thus
4the primary particle of/PM, more effectively improves cycle performance and high rate performance, improves the specific capacity of material.The present invention adopts ferric iron itself as the initator of polymerization reaction, does not need additionally to add initator.
After spray-dried, in high-temperature calcination heating process, be first coated on FePO
4there is thermal decomposition in the polymer P M of outside, polymer carbonization is also attended by gas generation; Lithium source and FePO subsequently
4and the carbon reaction after polymer carbonization generates final LiFePO
4/ C is also attended by CO
2or CO gas produces.The effusion of the various gases generated in whole heat treatment process can at FePO
4or LiFePO
4cavernous structure is gone out on surface, and the reaction in polymer and lithium source can make originally to occupy diminishing of position in addition, reserves certain space or hole, the final LiFePO forming cavernous structure
4/ C material.Prepared LiFePO
4the particle diameter of/C sample powder is about 50-80nm.
Preferred as such scheme: described iron derives from trivalent iron salt.
Preferred as such scheme: described source of iron is at least one in iron chloride, ferric nitrate.
Preferred as such scheme: described phosphorus derive from phosphoric acid, ammonium dihydrogen phosphate, ammonium hydrogen phosphate one or more.
Preferred as such scheme: lithium source is one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride.
Preferred as such scheme: according to mass ratio, carbon content is synthesis LiFePO
4the 2-10% of/C.
In such scheme: high-temperature burning process is: the presoma that spray-dried oven dry obtains is heated to 500 DEG C ~ 700 DEG C with the programming rate of 1 ~ 30 DEG C/min under inert atmosphere or reducing atmosphere, and constant temperature 5 ~ 15h, be cooled to room temperature again, obtained LiFePO after sieving
4/ C sample powder.
The invention has the beneficial effects as follows: compared with prior art, the present invention is by the poroid anode material of lithium battery LiFePO of in-situ polymerization cladding process synthesis nano
4/ C.The in-situ polymerization of the method limits growing up of primary sedimentation particle, is beneficial to preparation nanometer materials, and nano particle shortens the evolving path of lithium ion, relatively improves lithium ion diffusion rate.When high-temperature calcination, polymer is active coated, the carbon after carbonization and LiFePO
4contact closely, improve electronic conductivity, the cavernous structure formed during high-temperature calcination is simultaneously that electrolyte provides reservoir vessel, in charge and discharge process, no matter lithium ion is by exchange or mass transfer mode carries out lithium ion transport in lithium ion and electrolyte, all can improve the diffusion rate of lithium ion further.The process employs the synthetic method being easy to business-like solid liquid phase and combining, replacement source is drawn materials comparatively extensive, 50-80nm is about by the average grain diameter that is evenly distributed of sample particle after spraying dry and high-temperature calcination, prepared sample is dressed up battery first discharge specific capacity and can reach more than 165mAh/g, close to theoretical capacity 170mAh/g.The raising of electronic conductivity and the increase of lithium ion diffusion rate inherently improve the cycle performance (under 0.2C multiplying power circulate 50 times, capability retention is close to 100%) of material and large high rate performance (under 5C multiplying power after circulation 500 times capacity still up to 116mAh/g).The higher charge/discharge capacity of materials show of the method synthesis, good high rate performance and good circulation performance; Of the present invention simple to operate, technological process is short, and replacement source is drawn materials comparatively extensive, and cost of manufacture is relatively low.
Accompanying drawing explanation
Fig. 1 the present invention prepares the XRD figure of sample.
Fig. 2 the present invention prepares the scanning electron microscope (SEM) photograph of sample
Fig. 3 is circulation-specific volume under 0.2C multiplying power and coulombic efficiency figure.
Fig. 4 is the first charge-discharge figure under 0.2C multiplying power.
Fig. 5 is the step cycle graph under different multiplying
Fig. 6 is the circulation-specific volume figure under different multiplying.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Example 1:
Under intense agitation aniline monomer is joined the NH of 0.3M
4h
2pO
4in solution, subsequently by the FeCl of 0.3M
3solution, to add in above-mentioned solution, after reaction 5h, obtains the FePO that yellow fraction colour band point is green
4/ PANI presoma, afterwards by Li
2cO
3powder directly adds in above-mentioned presoma, vigorous stirring 2h on magnetic stirring apparatus, then spray-dried precursor powder, precursor powder is heated to 650 DEG C with the programming rate of 15 DEG C/min under an inert atmosphere (nitrogen), and constant temperature 5h, be cooled to room temperature again, the obtained poroid LiFePO of nanoscale after sieving
4/ C sample powder.Wherein NH
4h
2pO
4, FeCl
3, aniline and lithium carbonate addition meet: Li:Fe:P=1:1:1 (mol ratio), carbon content is synthesis LiFePO
45% (mass ratio) of/C.
Anode pole piece preparation process: by LiFePO
4/ C active substance, acetylene black, binding agent (Kynoar), be mixed evenly by the mass ratio of 90:5:5, furnishing starchiness, be evenly coated on 0.018mm aluminium foil.Then in 50 DEG C of baking ovens, take out to obtain positive plate after dry 12h, be then placed in the dry 10h of vacuum drying chamber, when temperature drops to 50 DEG C, be placed in rapidly glove box for subsequent use.
The assembling of battery: adopt metal lithium sheet as negative pole during assembled battery, Celgard 2400 barrier film, 1mol/L LiPF
6/ (EC+DEC+EMC) (volume ratio 1:1:1) is electrolyte, in the glove box being full of argon gas, carry out battery assembling.Load after assembling in valve bag, take out from glove box and fast compacting sealing.Electrochemical property test can be carried out after leaving standstill about 6h.The water content of glove box is about 0.1ppm, and oxygen content is about 0.5ppm.Finally on LAND cell tester, carry out charge-discharge performance test: charging/discharging voltage is 4.2 ~ 2.5V, probe temperature is 25 DEG C.Carry out charge-discharge test with 0.2C multiplying power, recording first discharge specific capacity is 168mAh/g, and after 50 circulations, capability retention is close to 100%; The capacity that to circulate under 5C multiplying power after 500 times is still up to 116mAh/g.The electric performance test figure under the XRD figure of prepared sample, scanning electron microscope (SEM) photograph, different multiplying is followed successively by referring to Fig. 1-6.
Embodiment 2
Under intense agitation pyrrole monomer is joined in the ammonium hydrogen phosphate solution of 0.3M, subsequently by the FeCl of 0.3M
3solution adds in above-mentioned solution, after reaction 7h, obtains the FePO of black
4/ PPy presoma, afterwards lithium acetate powder is directly added in above-mentioned presoma, vigorous stirring 1h on magnetic stirring apparatus, then spray-dried precursor powder, precursor powder is heated to 700 DEG C with the programming rate of 30 DEG C/min under an inert atmosphere (nitrogen), and constant temperature 5h, then be cooled to room temperature, the obtained poroid LiFePO of nanoscale after sieving
4/ C sample powder.Wherein Li:Fe:P=1:1:1 (mol ratio), carbon content is synthesis LiFePO
4/7% (mass ratio) of C.
Example 3
Under intense agitation acrylonitrile monemer is joined in the phosphoric acid solution of 0.3M, subsequently the iron nitrate solution of 0.3M is added in above-mentioned solution, after reaction 5h, obtain FePO
4/ PAN presoma, afterwards lithium hydroxide powder is directly added in above-mentioned presoma, vigorous stirring 2h on magnetic stirring apparatus, then spray-dried precursor powder, precursor powder is heated to 500 DEG C with the programming rate of 1 DEG C/min under an inert atmosphere (nitrogen), and constant temperature 15h, then be cooled to room temperature, the obtained poroid LiFePO of nanoscale after sieving
4/ C sample powder.Wherein Li:Fe:P=1:1:1 (mol ratio), carbon content is synthesis LiFePO
410% (mass ratio) of/C.
The present invention is not limited to above-described embodiment, if lithium source can also be one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.In a word, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (7)
1. a method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of in-situ polymerization, is characterized in that: be prepared as follows:
(1), by phosphorus source be dissolved in water and mix, under agitation joined by polymer monomer in above-mentioned mixed liquor, described polymer monomer is the one in aniline, pyrroles, acrylic acid, acrylonitrile, ethylene glycol, vinyl chloride, styrene;
(2) slowly add, again by source of iron solution in the mixed solution in step (1), be obtained by reacting precursor solution;
(3), by lithium source add in above-mentioned precursor solution, vigorous stirring, then spraying dry obtains precursor powder;
(4), above-mentioned precursor powder is obtained LiFePO through high-temperature calcination
4/ C.
2. the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of in-situ polymerization according to claim 1, is characterized in that: iron derives from solubility trivalent iron salt.
3. the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of in-situ polymerization according to claim 2, is characterized in that: iron comes from least one in iron chloride, ferric nitrate.
4. the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of in-situ polymerization according to claim 3, is characterized in that: phosphorus derive from phosphoric acid, ammonium dihydrogen phosphate, ammonium hydrogen phosphate one or more.
5. the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of in-situ polymerization according to claim 4, is characterized in that: lithium derives from as one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride.
6. the method for the coated synthesizing lithium ionic cell positive pole material lithium iron phosphate of in-situ polymerization as claimed in claim 1, is characterized in that: according to mass ratio, and carbon content is synthesis LiFePO
4the 2-10% of/C.
7. the method for the coated conjunction lithium ion battery anode material lithium iron phosphate of in-situ polymerization according to claim 6, it is characterized in that: high-temperature burning process is: the presoma that spray-dried oven dry obtains is heated to 500 DEG C ~ 700 DEG C with the programming rate of 1 ~ 30 DEG C/min under an inert atmosphere, and constant temperature 5 ~ 15h, be cooled to room temperature again, obtained LiFePO after sieving
4/ C sample powder.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105633369A (en) * | 2016-01-04 | 2016-06-01 | 兰州理工大学 | Preparation method of carbon-coated lithium iron phosphate material |
| CN109216664A (en) * | 2017-07-03 | 2019-01-15 | 中航信诺（营口）高新技术有限公司 | The preparation method of carbon-coated LiFePO 4 for lithium ion batteries |
| CN109698346A (en) * | 2018-12-29 | 2019-04-30 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN109728278A (en) * | 2018-12-29 | 2019-05-07 | 蜂巢能源科技有限公司 | Positive electrode active materials and preparation method thereof and lithium ion battery |
| CN110914194A (en) * | 2017-07-19 | 2020-03-24 | 纳诺万材料公司 | Improved synthesis of olivine-type lithium metal phosphate positive electrode materials |
| CN112086635A (en) * | 2020-08-31 | 2020-12-15 | 佛山市德方纳米科技有限公司 | Preparation method of lithium iron phosphate positive electrode active material |
| CN112290023A (en) * | 2020-10-21 | 2021-01-29 | 安徽清泉新能源科技集团有限责任公司 | Polypyrrole-doped power battery material and preparation method thereof |
| CN112397698A (en) * | 2020-11-16 | 2021-02-23 | 合肥国轩高科动力能源有限公司 | Composite conductive agent coated lithium iron phosphate material and preparation method and application thereof |
| CN113285071A (en) * | 2021-05-14 | 2021-08-20 | 合肥国轩高科动力能源有限公司 | Lithium iron phosphate and preparation method and application thereof |
| CN113337735A (en) * | 2021-05-27 | 2021-09-03 | 河北工业大学 | Nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources |
| CN113683072A (en) * | 2021-08-13 | 2021-11-23 | 内蒙古圣钒科技新能源有限责任公司 | Preparation method and application of spherical lithium iron phosphate cathode material |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105633369B (en) * | 2016-01-04 | 2017-11-07 | 兰州理工大学 | A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries material |
| CN105633369A (en) * | 2016-01-04 | 2016-06-01 | 兰州理工大学 | Preparation method of carbon-coated lithium iron phosphate material |
| CN109216664A (en) * | 2017-07-03 | 2019-01-15 | 中航信诺（营口）高新技术有限公司 | The preparation method of carbon-coated LiFePO 4 for lithium ion batteries |
| CN110914194A (en) * | 2017-07-19 | 2020-03-24 | 纳诺万材料公司 | Improved synthesis of olivine-type lithium metal phosphate positive electrode materials |
| CN109728278B (en) * | 2018-12-29 | 2021-04-20 | 蜂巢能源科技有限公司 | Positive active material, preparation method thereof and lithium ion battery |
| CN109728278A (en) * | 2018-12-29 | 2019-05-07 | 蜂巢能源科技有限公司 | Positive electrode active materials and preparation method thereof and lithium ion battery |
| CN109698346A (en) * | 2018-12-29 | 2019-04-30 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN112086635A (en) * | 2020-08-31 | 2020-12-15 | 佛山市德方纳米科技有限公司 | Preparation method of lithium iron phosphate positive electrode active material |
| CN112086635B (en) * | 2020-08-31 | 2022-01-07 | 佛山市德方纳米科技有限公司 | Preparation method of lithium iron phosphate positive electrode active material |
| CN112290023A (en) * | 2020-10-21 | 2021-01-29 | 安徽清泉新能源科技集团有限责任公司 | Polypyrrole-doped power battery material and preparation method thereof |
| CN112397698A (en) * | 2020-11-16 | 2021-02-23 | 合肥国轩高科动力能源有限公司 | Composite conductive agent coated lithium iron phosphate material and preparation method and application thereof |
| CN113285071A (en) * | 2021-05-14 | 2021-08-20 | 合肥国轩高科动力能源有限公司 | Lithium iron phosphate and preparation method and application thereof |
| CN113337735A (en) * | 2021-05-27 | 2021-09-03 | 河北工业大学 | Nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources |
| CN113337735B (en) * | 2021-05-27 | 2022-07-19 | 河北工业大学 | Nitrogen-doped carbon-packaged lithium ion sieve membrane electrode for electrochemical extraction of dissolved lithium resources |
| CN113683072A (en) * | 2021-08-13 | 2021-11-23 | 内蒙古圣钒科技新能源有限责任公司 | Preparation method and application of spherical lithium iron phosphate cathode material |
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Application publication date: 20150520 |