CN106784822A - A kind of high-voltage lithium ion batteries of volume energy density high - Google Patents
A kind of high-voltage lithium ion batteries of volume energy density high Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The present invention provides a kind of high-voltage lithium ion batteries of volume energy density high, belongs to technical field of lithium ion.The lithium ion battery includes positive plate and negative plate, and positive plate includes positive electrode and positive electrode binder, and negative plate includes negative material, and positive electrode includes iron manganese phosphate for lithium；Positive electrode binder is PVDF；Negative material is nanometer carbon plate/graphitized intermediate-phase carbosphere composite.The present invention uses LiFe1‑xMnxPO4As high-voltage anode material, reduce the rebound rate of positive plate thickness as positive electrode binder with the PVDF of low-molecular-weight, simultaneously using nanometer carbon plate/graphitized intermediate-phase carbosphere composite as negative material, using height ratio capacity, make the use of negative material less, the thickness of negative plate and battery is reduced, the volume energy density of battery is substantially increased；And increase conducting film on the aluminium foil of positive plate, the internal resistance of battery can be effectively reduced.
Description
【Technical field】
A kind of technical field of lithium ion of the present invention, and in particular to the high-voltage lithium ion electricity of volume energy density high
Pond.
【Background technology】
As electronic product is constantly developed, lithium ion battery is used widely, and present electronic product is continuous
Update, while requirement to lithium ion battery product also more and more higher.At present in whole battery industry, each battery
The product quality of producer differs, 90% producer all in low and middle-end horizontality, on the electronic product to some high requests,
Battery performance can not meet requirement, for example：In early stage mainly based on bluetooth, be not to the performance requirement of battery it is very high, only
The enterprise for having certain fund can put into lithium ion battery industry, and from the point of view of current market, main electronics is produced
Product are number, panel computer, ultra thin handset, and electronic product is all that touch-screen shows, such product, because being limited by volume
Lithium ion battery is asked to be higher by much than traditional lithium-ion battery in volume and capacity ratio, such as Samsung part type trumpeter's machine is in same volume
Under, Capacity Ratio that it is required it is conventional be higher by about 12% or so, with the technical merit of present each producer, being extremely difficult to this will
Ask, therefore, capacity polymer Li-ion battery higher, it has also become the first-selection of digital communication class product.
With the arriving in 3G/4G epoch, present most of communication product possess online, play games, see e-book,
Various functions such as MP3, MP4, so to the capacity requirement more and more higher of lithium ion battery.Common polymer Li-ion battery is received
The influence of its material property, can not meet the demand of some special populations on capacity, it is therefore necessary to develop a kind of high power capacity
The digital communication polymer Li-ion battery of type.
The lithium ion cell positive gram volume that in the market is used plays only 142 MAhs/g, to current intelligence hand
Machine, the screen maximization of panel computer has been difficult to meet and has required, scientific and technological demand for development we to must provide for volume ratio higher
Lithium ion battery.To the performance of lithium ion battery, especially energy density and power density propose requirement higher to people.Electricity
The energy density in pond is relevant with the specific capacity of battery and operating voltage, therefore seeks the lithium ion battery of high voltage and Large Copacity just
Pole material has very important significance.The anode material for lithium-ion batteries for using at present, such as LiCoO2、LiMn2O4、
LiFePO4、LiNixCoyMn1-x-yO2Operating voltage be below 4V, the energy density and power density of battery are subject in application
Limitation.
Therefore 4.5V high-voltage anode materials LiFe1-xMnxPO4Appearance it is just significant.High-tension feature is not
But energy density and power density can be improved, and improves the performance of cell, so that the monomer of series connection needed for reducing
The quantity of battery, advantage is brought to battery performance safety and cost.
【The content of the invention】
Goal of the invention of the invention is：To solve above-mentioned problem, it is an object of the invention to provide a kind of high
The high-voltage lithium ion batteries of volume energy density, not only with high-voltage anode material LiFe1-xMnxPO4Electricity is improved to reach
Tankage, and the capacity of battery is improved in terms of battery process and other materials, to reach comprehensive lifting lithium ion battery
Volume energy density.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of high-voltage lithium ion batteries of volume energy density high of the present invention, including positive plate and negative plate, it is described just
Pole piece includes positive electrode and positive electrode binder, and the negative plate includes negative material, and the positive electrode includes iron manganese phosphate
Lithium, and the ferrimanganic ratio of lithium manganese phosphate is 0.1~0.35:0.65~0.90；The positive electrode binder is PVDF, and molecular weight is 30
~70 ten thousand；The negative material is nanometer carbon plate/graphitized intermediate-phase carbosphere composite, and nanometer carbon plate is three-dimensional class stone
Black alkene nanometer sheet.The discharge platform of iron manganese phosphate for lithium is in 3.9V or so, and gram volume of the iron manganese phosphate for lithium under 1.0C multiplying powers
In more than 144mAh/g, advantage is had more compared to LiFePO4 in terms of electrical property, control the iron manganese content of iron manganese phosphate for lithium
Than the platform voltage influence on battery too high of Fe contents is larger, and iron content is too low, and the conductance of material is again too low, influences on the contrary
The performance of capacity.The molecular weight of the PVDF that positive electrode binder is used on the market at present is more than 700,000 molecular weight, positive pole material
Material is coated into positive plate again by rolling, and after PVDF solidifications, the bounce-back of pole piece thickness is larger, and the molecular weight of PVDF is bigger, pole
Bounce-back value is also bigger after the rolling of piece thickness and after discharge and recharge, easily causes cell thickness and becomes big and then increase whole volume, makes
Into volume energy density reduction；And using the PVDF of low-molecular-weight, can effectively reduce the bounce-back after positive plate rolling, also can
The thickness bounce-back of pole piece, so as to reduce the thickness of battery, improves the volume energy density of battery after attenuating battery charging and discharging.
Positive plate of the present invention also includes there be one layer of conducting film between aluminium foil, and positive electrode and aluminium foil, described to lead
The thickness of electrolemma is 1~3 μm.
The preparation method of nanometer carbon plate of the present invention/graphitized intermediate-phase carbosphere composite is comprised the following steps：
(1) the clean round-bottomed flasks of 1000mL are taken, the concentrated sulfuric acid of 200mL98% is added, it is 2~8 to control bottle reaction temperature
DEG C, mechanical agitation adds graphitized intermediate-phase carbosphere 8g, slowly repeatedly adds 1.0~4.0g sodium nitrate, last slow multiple
Potassium permanganate is added, 2~5h is reacted；
(2) reaction temperature is increased to 30~40 DEG C, after continuing to stir 1~5h, 60~100 DEG C is added under agitation
Deionized water 400mL, then heighten heating-up temperature to 85~105 DEG C, the mass fraction for adding 150mL is 10% H2O2, continue
3~7h of stirring, reaction terminates；
(3) use quality fraction is that 10% HCl solution washed once, then is washed with deionized to neutrality, and vacuum is taken out
Drying in 80~100 DEG C of baking ovens is put into after filter, graphitized intermediate-phase carbosphere intermediate is obtained；
(4) graphitized intermediate-phase carbosphere intermediate is put under 800~1100 DEG C of oxygen free condition and is reduced in high temperature, most
A nanometer carbon plate/graphitized intermediate-phase carbosphere composite is obtained eventually.
Negative material of the present invention uses nanometer carbon plate/graphitized intermediate-phase carbosphere composite, wherein in the middle of graphitization
The capacity of phase carbosphere plays general in 360mAh/g, and after the method for the present invention is processed, graphitized intermediate-phase carbosphere
Between again increased class graphene-structured composition, substantially increase negative material capacity play, and with potassium permanganate with
The weight of graphitized intermediate-phase carbosphere is than change, and the nanometer carbon plate for obtaining/graphitized intermediate-phase carbosphere composite is maximum
Capacity play and can reach more than 2000, than being higher by more than 5 times with graphitized intermediate-phase carbosphere, therefore, production is same
The lithium ion battery of capacity, the consumption using nanometer carbon plate/graphitized intermediate-phase carbosphere composite is less, also just subtracts significantly
Small accounting of the cathode pole piece in battery volume, thus the volume of battery is substantially reduced, improve the volume energy of battery
Density.
Positive plate of the invention first adheres to one layer of conducting film before positive electrode is coated with aluminium foil, and the conducting film can be with
By weight than 95~98:2~5 Graphene and the PVDF are constituted, and with electrostatic spraying on aluminium foil；Can also be by Graphene
Constitute, and conducting film is attached on aluminium foil using vapour deposition process.Because the conductive capability of Graphene is very strong, made using Graphene
It is conducting film, the electrical conductivity of positive plate can be increased, reduce internal resistance, improve the performance of positive electrode capacity, and then reaches lifting
The effect of battery capacity.
The weight of potassium permanganate of the present invention and graphitized intermediate-phase carbosphere is than 1~3:1, the energy of oxidation of potassium permanganate
Power is strong, and the oxidation of coal on graphitized intermediate-phase carbosphere surface can be made the composition of class Graphene, greatly improves negative pole
The energy density of material.
In sum, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：The present invention uses LiFe1- xMnxPO4As high-voltage anode material, the bounce-back of positive plate thickness is reduced as positive electrode binder with the PVDF of low-molecular-weight
Rate, while using nanometer carbon plate/graphitized intermediate-phase carbosphere composite as negative material, using the height ratio of negative material
Capacity, makes the use of negative material less, reduces the thickness of negative plate, and then reduces the thickness of battery, substantially increases
The volume energy density of battery；And increase conducting film on the aluminium foil of positive plate, the internal resistance of battery can be effectively reduced,
The energy loss of battery charge or discharge is reduced, the utilization rate of the energy content of battery is improve.
【Specific embodiment】
Below by way of specific embodiment and tables of data, the invention will be further described.
Embodiment 1
A kind of high-voltage lithium ion batteries of volume energy density high, including positive plate and negative plate, wherein positive plate bag
Positive electrode and positive electrode binder are included, negative plate includes negative material, and positive electrode includes iron manganese phosphate for lithium in battery of the present invention,
And the ferrimanganic ratio of lithium manganese phosphate is 0.1:0.90；Positive electrode binder used is PVDF, and molecular weight is 30~500,000；Positive plate
Also include there be one layer of conducting film between aluminium foil, and positive electrode and aluminium foil, the thickness of the conducting film is 1~3 μm.Positive plate
Before positive electrode is coated with, one layer of conducting film is first adhered on aluminium foil, the conducting film can compare 95 by weight:5 Graphene and
The PVDF compositions, and with electrostatic spraying on aluminium foil；The negative material is multiple for nanometer carbon plate/graphitized intermediate-phase carbosphere
Condensation material, and nanometer carbon plate is three-dimensional class graphene nanometer sheet.
Negative material nanometer carbon plate/graphitized intermediate-phase carbosphere composite of the invention is by graphitized intermediate-phase carbon
Microballoon prepares gained, and its preparation method is comprised the following steps：
(1) the clean round-bottomed flasks of 1000mL are taken, the concentrated sulfuric acid of 200mL98% is added, bottle reaction temperature is controlled for 2 DEG C,
Mechanical agitation adds graphitized intermediate-phase carbosphere 8g, slow repeatedly to add 1.0g sodium nitrate, finally slow repeatedly to add Gao Meng
Sour potassium, reacts 2h；
(2) reaction temperature is increased to 30 DEG C, after continuing to stir 1h, 60 DEG C of deionized water is added under agitation
400mL, then heating-up temperature to 85 DEG C is heightened, the mass fraction for adding 150mL is 10% H2O2, continue to stir 3h, reaction knot
Beam；
(3) use quality fraction is that 10% HCl solution washed once, then is washed with deionized to neutrality, and vacuum is taken out
Drying in 80~100 DEG C of baking ovens is put into after filter, graphitized intermediate-phase carbosphere intermediate is obtained；
(4) graphitized intermediate-phase carbosphere intermediate is put under 800 DEG C of oxygen free condition and is reduced in high temperature, finally given
Nanometer carbon plate/graphitized intermediate-phase carbosphere composite.
In the preparation process of the negative material, potassium permanganate compares 1.25 with the weight of graphitized intermediate-phase carbosphere:1.
Embodiment 2
A kind of high-voltage lithium ion batteries of volume energy density high, including positive plate and negative plate, wherein positive plate bag
Positive electrode and positive electrode binder are included, negative plate includes negative material, and positive electrode includes iron manganese phosphate for lithium in battery of the present invention,
And the ferrimanganic ratio of lithium manganese phosphate is 0.35:0.65；Positive electrode binder used is PVDF, and molecular weight is 50~700,000；Positive pole
Piece also includes there be one layer of conducting film between aluminium foil, and positive electrode and aluminium foil, and the thickness of the conducting film is 1~3 μm.Positive pole
Piece first adheres to one layer of conducting film before positive electrode is coated with aluminium foil, and the conducting film can compare 98 by weight:2 Graphene
Constituted with the PVDF, and with electrostatic spraying on aluminium foil；The negative material is nanometer carbon plate/graphitized intermediate-phase carbosphere
Composite, and nanometer carbon plate is three-dimensional class graphene nanometer sheet.
Negative material nanometer carbon plate/graphitized intermediate-phase carbosphere composite of the invention is by graphitized intermediate-phase carbon
Microballoon prepares gained, and its preparation method is comprised the following steps：
(1) the clean round-bottomed flasks of 1000mL are taken, the concentrated sulfuric acid of 200mL98% is added, bottle reaction temperature is controlled for 8 DEG C,
Mechanical agitation adds graphitized intermediate-phase carbosphere 8g, slow repeatedly to add 4.0g sodium nitrate, finally slow repeatedly to add Gao Meng
Sour potassium, reacts 5h；
(2) reaction temperature is increased to 40 DEG C, after continuing to stir 5h, 100 DEG C of deionized water is added under agitation
400mL, then heating-up temperature to 105 DEG C is heightened, the mass fraction for adding 150mL is 10% H2O2, continue to stir 7h, reaction knot
Beam；
(3) use quality fraction is that 10% HCl solution washed once, then is washed with deionized to neutrality, and vacuum is taken out
Drying in 80~100 DEG C of baking ovens is put into after filter, graphitized intermediate-phase carbosphere intermediate is obtained；
(4) graphitized intermediate-phase carbosphere intermediate is put under 1100 DEG C of oxygen free condition and is reduced in high temperature, final
To nanometer carbon plate/graphitized intermediate-phase carbosphere composite.
In the preparation process of the negative material, potassium permanganate compares 1.75 with the weight of graphitized intermediate-phase carbosphere:1.
Embodiment 3
A kind of high-voltage lithium ion batteries of volume energy density high, including positive plate and negative plate, wherein positive plate bag
Positive electrode and positive electrode binder are included, negative plate includes negative material, and positive electrode includes iron manganese phosphate for lithium in battery of the present invention,
And the ferrimanganic ratio of lithium manganese phosphate is 0.2:0.8；Positive electrode binder used is PVDF, and molecular weight is 50~700,000；Positive plate
Also include there be one layer of conducting film between aluminium foil, and positive electrode and aluminium foil, the thickness of the conducting film is 1~3 μm.Positive plate
Before positive electrode is coated with, one layer of conducting film is first adhered on aluminium foil, the conducting film can be made up of Graphene, and conducting film profit
It is attached on aluminium foil with vapour deposition process.The negative material is nanometer carbon plate/graphitized intermediate-phase carbosphere composite, and
Nanometer carbon plate is three-dimensional class graphene nanometer sheet.
Negative material nanometer carbon plate/graphitized intermediate-phase carbosphere composite of the invention is by graphitized intermediate-phase carbon
Microballoon prepares gained, and its preparation method is comprised the following steps：
(1) the clean round-bottomed flasks of 1000mL are taken, the concentrated sulfuric acid of 200mL98% is added, bottle reaction temperature is controlled for 5 DEG C,
Mechanical agitation adds graphitized intermediate-phase carbosphere 8g, slow repeatedly to add 2.5g sodium nitrate, finally slow repeatedly to add Gao Meng
Sour potassium, reacts 3.5h；
(2) reaction temperature is increased to 35 DEG C, after continuing to stir 3h, 80 DEG C of deionized water is added under agitation
400mL, then heating-up temperature to 95 DEG C is heightened, the mass fraction for adding 150mL is 10% H2O2, continue to stir 5h, reaction knot
Beam；
(3) use quality fraction is that 10% HCl solution washed once, then is washed with deionized to neutrality, and vacuum is taken out
Drying in 80~100 DEG C of baking ovens is put into after filter, graphitized intermediate-phase carbosphere intermediate is obtained；
(4) graphitized intermediate-phase carbosphere intermediate is put under 950 DEG C of oxygen free condition and is reduced in high temperature, finally given
Nanometer carbon plate/graphitized intermediate-phase carbosphere composite.
In the preparation process of the negative material, potassium permanganate compares 2.25 with the weight of graphitized intermediate-phase carbosphere:1.
Compliance test result：
As a example by the 856068 model lithium ion batteries with capacity as 4000mAh.The standard size of battery battery core is thickness
7.6mm, width 50.0mm, length 68.0mm, the normal volume energy of the positive electrode correspondence battery of present invention iron manganese phosphate for lithium
Metric density is 426.7Wh/L.
Experimental group：Experimental group carries out assembled battery and is tested using the material and its composition of embodiment 1~3, battery
Packaging technology is as follows:
(1) preparation of positive pole：Iron manganese phosphate for lithium is positive active material, and super conductive carbon black (SP) is conductive agent, gathers inclined
PVF (PVDF) is binding agent, and N- dimethyl pyrrolidones (NMP) are solvent.Prepare slurry viscosity be controlled to 2000~
8500mPa·s.Mass percent used by the present embodiment is iron manganese phosphate for lithium：SP：PVDF=97:1.4:1.6.First by PVDF
It is substantially soluble in NMP and is made glue, continue to add SP stirring, is eventually adding after iron manganese phosphate for lithium persistently stirs and takes out true
Sky, removes the bubble in slurry.Last being coated in gained slurry double-faced uniform on the aluminium foil of 12 μ m thicks.Through drying, roller
Pressure, carries out tab welding after cut-parts, lug thickness is 0.1mm.Positive plate is completed to make.
(2) preparation of negative pole：To make HGMCMB as negative electrode active material by oneself, conductive agent is the acetylene black of high conductivity, is glued
Knot agent is the composition of aqueous butadiene-styrene rubber breast SBR and sodium carboxymethylcellulose CMC, and water is solvent.Prepare slurry viscosity control
It is 1000~4500mPas.Mass percent used by the present embodiment is HGMCMB：AB：CMC：SBR=96.5:1:1:1.5.It is first
First CMC is substantially soluble in glue is made in water, continued addition AB and stir, be persistently stirring evenly and then adding into HGMCMB is added
SBR stirs 1.5h, vacuumizes, and removes the bubble in slurry.Gained slurry double-faced uniform is finally coated in 8 μ m thick Copper Foils
On.Through drying, roll-in carries out tab welding after cut-parts, lug thickness is 0.1mm.Negative plate is completed to make.
(3) battery assembling：Barrier film uses thickness for 12 μm of microporous polyethylene film.Plastic-aluminum film thickness is 113 μm.To prepare
Good positive and negative plate and membrane winding into core, is once encapsulated, fluid injection and is packaged, complete through chemical conversion, secondary encapsulation
Made into battery.
Control group：Assembling test is carried out with the battery with experimental group same model.The material of control group is identical with experimental group
Iron manganese phosphate for lithium and graphitized intermediate-phase carbosphere, positive plate make when, the molecular weight of positive electrode binder is respectively 70~100
Ten thousand and 100~1,200,000 PVDF, material it is identical with experimental group with when consumption, and aluminium foil does not adhere to any conducting film first
Routinely technique is directly coated with positive electrode, and the assembling of battery is carried out according to experimental group.
For convenience of contrasting, the other specification of control group is identical with experimental group, and concrete outcome is shown in Table shown in 1 and 2：
The thickness rebounded before thickness and pole piece coiling after the rolling of the pole piece of table 1
| Anode pole piece thickness/mm after rolling | Cathode pole piece thickness/mm after rolling | Positive plate thickness/mm before winding | Negative plate thickness/mm before winding | Positive plate rebound rate | |
| Embodiment 1 | 0.194 | 0.089 | 0.201 | 0.105 | 3.61% |
| Embodiment 2 | 0.195 | 0.043 | 0.205 | 0.051 | 5.13% |
| Embodiment 3 | 0.194 | 0.027 | 0.203 | 0.032 | 4.64% |
| Control group 1 | 0.195 | 0.112 | 0.210 | 0.131 | 7.69% |
| Control group 2 | 0.195 | 0.112 | 0.223 | 0.130 | 14.36% |
As can be seen from Table 1：The molecular weight of positive electrode binder PVDF is bigger, and the rebound rate of positive plate is bigger, causes pole piece
It is thicker, the integral thickness of battery is influenceed, and then reduce the volume energy density of battery；And the thickness of negative plate is also with Gao Meng
The weight of sour potassium and graphitized intermediate-phase carbosphere than increase and reduce.
The battery parameter contrast of the control group of table 2 and experimental group
As can be seen from Table 1 and Table 2：Graphite is used using nanometer carbon plate/graphitized intermediate-phase carbosphere composite ratio
Battery volume energy density obtained in change carbonaceous mesophase spherules is higher, and the negative material for needing is more preferably, cathode pole piece thickness
It is thinner；In addition, increasing conducting film on aluminium foil, the internal resistance of cell can be reduced.
Claims (6)
1. a kind of high-voltage lithium ion batteries of volume energy density high, including positive plate and negative plate, the positive plate include
Positive electrode and positive electrode binder, the negative plate include negative material, it is characterised in that the positive electrode includes manganese phosphate
Iron lithium, and the ferrimanganic ratio of lithium manganese phosphate is 0.1~0.35:0.65~0.90；The positive electrode binder is PVDF, and molecular weight is
30~700,000；The negative material is nanometer carbon plate/graphitized intermediate-phase carbosphere composite, and nanometer carbon plate is three-dimensional class
Graphene nanometer sheet.
2. a kind of high-voltage lithium ion batteries of volume energy density high according to claim 1, it is characterised in that it is described just
Pole piece also includes there be one layer of conducting film between aluminium foil, and positive electrode and aluminium foil, and the thickness of the conducting film is 1~3 μm.
3. a kind of high-voltage lithium ion batteries of volume energy density high according to claim 1, it is characterised in that described to receive
The preparation method of rice carbon plate/graphitized intermediate-phase carbosphere composite is comprised the following steps：
(1) the clean round-bottomed flasks of 1000mL are taken, the concentrated sulfuric acid of 200mL98% is added, it is 2~8 DEG C, machine to control bottle reaction temperature
Tool stirring adds graphitized intermediate-phase carbosphere 8g, slow multiple addition 1.0~4.0g sodium nitrate, last slow repeatedly addition height
Potassium manganate, reacts 2~5h；
(2) reaction temperature is increased to 30~40 DEG C, after continuing to stir 1~5h, under agitation adds 60~100 DEG C to go
Ionized water 400mL, then heating-up temperature to 85~105 DEG C is heightened, the mass fraction for adding 150mL is 10% H2O2, continue to stir
3~7h, reaction terminates；
(3) use quality fraction is that 10% HCl solution washed once, then is washed with deionized to neutrality, after vacuum filtration
Drying in 80~100 DEG C of baking ovens is put into, graphitized intermediate-phase carbosphere intermediate is obtained；
(4) graphitized intermediate-phase carbosphere intermediate is put under 800~1100 DEG C of oxygen free condition and is reduced in high temperature, final
To nanometer carbon plate/graphitized intermediate-phase carbosphere composite.
4. a kind of high-voltage lithium ion batteries of volume energy density high according to claim 2, it is characterised in that described to lead
Electrolemma is by weight than 95~98:2~5 Graphene and the PVDF are constituted, and with electrostatic spraying on aluminium foil.
5. a kind of high-voltage lithium ion batteries of volume energy density high according to claim 2, it is characterised in that described to lead
Electrolemma is made up of Graphene, and conducting film is attached on aluminium foil using vapour deposition process.
6. a kind of high-voltage lithium ion batteries of volume energy density high according to claim 3, it is characterised in that the height
The weight of potassium manganate and graphitized intermediate-phase carbosphere is than 1~3:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108963261A (en) * | 2018-07-17 | 2018-12-07 | 河南电池研究院有限公司 | A kind of lithium ion cell positive binder and its application |
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| CN106784822B (en) | 2020-08-25 |
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