CN104993174B - A kind of preparation method of lithium ion battery negative material - Google Patents
A kind of preparation method of lithium ion battery negative material Download PDFInfo
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- CN104993174B CN104993174B CN201510308187.6A CN201510308187A CN104993174B CN 104993174 B CN104993174 B CN 104993174B CN 201510308187 A CN201510308187 A CN 201510308187A CN 104993174 B CN104993174 B CN 104993174B
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of lithium ion battery negative material, belong to technical field of lithium ion.The preparation method of the lithium ion battery negative material comprises the following steps：Graphite and oxidant, organic acid reaction are obtained into intercalated graphite, intercalated graphite is added in NaOH solution, is soaked, is washed, is crushed, spheroidization processing is produced.The lithium ion battery negative material of the present invention is handled intercalated graphite by infusion method, is reduced the ungraphitised carbon and surface impurity of graphite surface, is reduced the lithium ion of non reversibility carbon consumption, so as to improve the first charge-discharge efficiency of graphite.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, belong to technical field of lithium ion.
Background technology
In each battery material that lithium ion battery is used, negative material is influence battery capacity and cycle performance most heavy
One of factor wanted.At present, use most ripe negative material is graphite material, including native graphite, Delanium etc., wherein
Native graphite in lithium ion battery manufacture field with preferable charge-discharge performance and relatively low cost due to having obtained big rule
The application of mould.
But, the Coating combination of native graphite can be only 16.7kJ/mol, during repeated charge, and graphite synusia holds
It is easily peelable, cause the structure of negative material to change, influence the normal deintercalation of lithium ion, ultimately result under cycle performance of battery
Drop is than more serious.Find in actual applications, lithium ion battery prepared by native graphite, first charge-discharge efficiency is poor, it is former
During because that may be first charge-discharge, graphite material structural collapse result in expendable capacitance loss.Moreover, native graphite by
It is smaller in interlamellar spacing, Li+Smaller in the diffusion rate of graphite layers, the high rate during charging-discharging of material is relatively low, it is impossible to meet
Requirement of the electrical source of power for power characteristic and energy density.
In order to improve the chemical property of native graphite, generally using the method to modifying natural graphite, microdilatancy is modified
It is exactly one of which method of modifying.Microdilatancy is modified the general means used physically or chemically, by graphite slight expansion, makes its layer
Spacing increases.This modification can both improve diffusion rate of the lithium ion in graphite layers, can alleviate graphite cathode again
Structure change during embedding de- lithium, improves its cyclical stability.
Zheng Yongping (ZOU Lin, KANG Fei-Yu, ZHENG Yong-Ping, et al.Modified natural
flake graphite with high cycle performance as anode material in lithium ion
batteries.Electrochimica Acta,2009,54(15):3930-3934.) etc. first prepare sulfuric acid-graphite layers
Compound, 24h is heated at 360 DEG C and slowly takes off slotting, then the Graphite Coating resin carbon after de- insert, prepared resin charcoal bag
Cover microdilatancy graphite cathode material under 0.2C multiplying powers specific discharge capacity up to 378mAh/g, after being circulated through 100 times, capacity is almost
Do not decay.But this method is complex, and among the experiment, Spherical graphite particles cracking, ball shape and structure is broken
It is bad, reduce the energy density per unit volume of battery.
Publication No. CN104157863A Chinese invention patent (date of publication is on November 19th, 2014) discloses one kind
The preparation method of microdilatancy graphite cathode material, and specifically disclose utilization LITHIUM BATTERY powder graphite material, oxidant, intercalator
According to mass ratio 1:0.05-1:0.5-10 is mixed, and 10-40 DEG C of oxidation intercalation 30-60min, room temperature filters to isolate solids, washed
It is 6-7 to wash to pH, and 200-800 DEG C of expanded 1-30min under inert atmosphere after drying, insulation obtains microdilatancy graphite.In the patent
Obtained microdilatancy graphite expansion multiple is 2-10 times, and graphite layers are away from increasing substantially.This method is simple to operation, but should
Scheme easily causes the problem of graphite material first charge-discharge efficiency is relatively low when preparing microdilatancy graphite using organic acid, its
Reason may be easy to electrolyte for the unnecessary hydroxyl or carboxyl and its polymer residues of graphite surface and occur side reaction, cause
First charge-discharge is reduced.
The content of the invention
It is an object of the invention to provide a kind of preparation of the higher lithium ion battery negative material of first charge-discharge efficiency
Method.
In order to realize the above object the technical scheme of the lithium ion battery negative material of the present invention is as follows：
A kind of preparation method of lithium ion battery negative material, comprises the following steps：
Graphite and oxidant, organic acid reaction are obtained into intercalated graphite, intercalated graphite is added in NaOH solution, immersion,
Washing, is crushed, spheroidization processing, is produced.
The lithium ion battery negative material of the present invention improves stone by the way that intercalated graphite addition NaOH solution is soaked
The mobility of lithium ion in ink, can make its mobility ratio native graphite improve 1.5 times, meanwhile, NaOH solution immersion can be notable
Graphite carrier concentration is reduced, weakens p-type doping.Due to the hydroxyl and the carboxyl reaction of graphite surface in sodium hydroxide, reduction
The reaction probabilities of oxy radical and electrolyte, while the sodium ion introduced is conducive to the Stability Analysis of Structures of clad, improve its surface
Structural stability, and then greatly improve the first charge-discharge efficiency of material.
Spheroidization processing is by material in irregular shape polishing glomeration or approximate sphericity, so as to improve the stream of material
Dynamic property, loose thickness and its specific surface area.It can specifically be polished using spheroidization equipment such as balling machine.
In order to improve the hydroxide that the efficiency of graphite immersion treatment in sodium hydroxide solution avoids excessive concentrations simultaneously again
The concentration that sodium produces NaOH solution in influence, the present invention on graphite-structure is preferably 0.5~1.0g/L.
To ensure the effect of graphite immersion, carried out at a temperature of being immersed in 20-60 DEG C, soak time is 5-30min.
In order to improve NaOH and the intercalated graphite in the effect of naoh treatment graphite, the present invention in NaOH solution
Mass ratio be：mNaOH：mGraphite=1：1~10.
Intercalated graphite in the present invention can use intercalated graphite of the prior art, in order to further improve lithium-ion electric
The preparation method of intercalated graphite in the first charge-discharge efficiency of pond negative material, the present invention comprises the following steps：
1) by graphite, oxidant, organic acid with mass ratio 1：(3~5)：(1~3) mix, reacted at a temperature of 20-60 DEG C
0.5-4h, is washed to pH=6-7,60-100 DEG C of drying obtains powders A by the obtained mixture that obtains；
2) powders A is warming up to 600-900 DEG C, is incubated 1-4h, produces.
Intercalated graphite prepared by the above method slightly increases due to having carried out micro- expansion layer processing, the average interlamellar spacing of graphite,
The activation energy that graphite takes off lithium reaction is reduced, and intercalation potential slightly has raising, and lithium ion is easier to deviate from from graphite layers, first
Efficiency for charge-discharge and high rate performance are improved.
Graphite in the present invention can be preferably crystalline flake graphite, ball-type graphite, and by spheroidization processing.
The oxidant used in the present invention can be preferably one kind in hydrogen peroxide, potassium permanganate, ammonium nitrate.It is preferred that making
Use hydrogen peroxide.
In order to improve to effect of the graphite layers away from increase, the organic acid in the present invention be preferably ethanedioic acid, succinic acid, oneself
One kind in diacid, tartaric acid, benzoic acid, citric acid or laurate.
In order that heating when intercalated graphite structure change it is more steady, the present invention in step 2) in heating speed control be
1~3 DEG C/min.
The lithium ion battery negative material of the present invention is handled intercalated graphite by infusion method, reduces graphite surface
Ungraphitised carbon and surface impurity, the lithium ion of non reversibility carbon consumption is reduced, so as to improve the charge and discharge first of graphite
Electrical efficiency.
Further, the present invention is used as intercalator preparation intercalated graphite by organic acid, protects the spheroidization pattern of graphite
It is not destroyed in processing procedure, graphite layers are away from d002Slightly increase, average grain size Lc, La reduce, graphite particle surface
It is more smooth, the active site of material and the ratio of ungraphitised carbon are reduced, the first charge-discharge effect of material is further increased
Rate.
The micro- processing of expansion layer and immersion treatment combination, have significant effect, greatly to the ungraphitised carbon for removing graphite surface
The big first charge-discharge efficiency for improving material.Moreover, the preparation method of the intercalated graphite of the present invention can be soaking with sodium hydroxide
Step improves constitutionally stable intercalated graphite, and soaking with sodium hydroxide can remove the residual left in intercalated graphite preparation process and gather again
Compound, the two synergy has finally given Stability Analysis of Structures, first charge-discharge efficiency very high negative electrode of lithium ion battery material
Material.
Lithium ion battery negative material D prepared by the present invention10For 4~6 μm, D50For 10~14 μm, D90For 28~32 μm,
DminFor 0.5~1.5 μm, Dmax≤ 45 μm, 1.40~1.70g/m2 of compacted density, 2.5~4.5m of specific surface area2/ g, mobility
≥1200m3/ VS, interlamellar spacing D002>=0.3380nm, first discharge capacity >=350mAh/g, discharging efficiency >=94% first, times
Rate performance：8.0C discharges after 0.3C chargings, capability retention >=91%.
Brief description of the drawings
Fig. 1 schemes for the SEM of the lithium ion battery negative material of the embodiment of the present invention 1；
Fig. 2 be 1-3 of the embodiment of the present invention in lithium ion battery negative material discharge voltage-specific capacity curve map；
The multiplying power and cycle performance curve for the battery that Fig. 3 is prepared for the lithium ion battery negative material of the embodiment of the present invention 1
Figure；
The multiplying power and cycle performance curve map for the battery that Fig. 4 is prepared for the negative material in comparative example.
Embodiment
Technical scheme is illustrated with reference to specific embodiment.
Embodiment 1
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) spheroidization crystalline flake graphite 10g, oxidants hydrogen peroxide 40g, organic acid ethanedioic acid 20g are mixed, the spheroidization
The particle diameter D of crystalline flake graphite50=30 μm, phosphorus content is 99.96wt%, at a temperature of 40 DEG C, stirring, reacts 2h, by obtaining for obtaining
Mixture is washed to pH=6, is dried at a temperature of 80 DEG C, obtains powders A；
2) powders A is sent into Muffle furnace, 800 DEG C is warming up to 2 DEG C/min heating rate, be incubated 2h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) intercalated graphite made from 5g is added into concentration in 0.75g/L NaOH solution, NaOH solution is by NaOH1g, two
Secondary distilled water 1330g is formulated, and the mass ratio of NaOH and intercalated graphite in NaOH solution are：mNaOH：mGraphite=1：5,40
At a temperature of DEG C, soak 10min, using redistilled water clean 3 times, crush, carry out spheroidization processing with balling machine, produce lithium from
Sub- cell negative electrode material.
Embodiment 2
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) the spherical graphite 10g of spheroidization, oxidants hydrogen peroxide 30g, organic acid succinic acid 10g are mixed, this is spherical
Change the particle diameter D of spherical graphite50=40 μm, phosphorus content is 99.96wt%, at a temperature of 20 DEG C, stirring, 4h is reacted, by what is obtained
Obtain mixture and be washed to pH=7, dried at a temperature of 60 DEG C, obtain powders A；
2) powders A is sent into Muffle furnace, 600 DEG C is warming up to 1 DEG C/min heating rate, be incubated 4h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) intercalated graphite made from 10g is added into concentration in 0.5g/L NaOH solution, NaOH solution is by NaOH1g, two
Secondary distilled water 2000g is formulated, and the mass ratio of NaOH and intercalated graphite in NaOH solution are：mNaOH：mGraphite=1：10,
At a temperature of 20 DEG C, 30min is soaked, is cleaned 3 times using redistilled water, is crushed, is carried out spheroidization processing with balling machine, produce lithium
Ion battery cathode material.
Embodiment 3
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) spheroidization crystalline flake graphite 10g, oxidants hydrogen peroxide 50g, organic acid adipic acid 30g are mixed, the spheroidization
The particle diameter D of crystalline flake graphite50=50 μm, phosphorus content is 99.96wt%, at a temperature of 60 DEG C, stirring, 0.5h is reacted, by what is obtained
Obtain mixture and be washed to pH=6, dried at a temperature of 100 DEG C, obtain powders A；
2) powders A is sent into Muffle furnace, 900 DEG C is warming up to 3 DEG C/min heating rate, be incubated 1h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) by made from 1.0g intercalated graphite add concentration for 1.0g/L NaOH solution in, NaOH solution by NaOH1g,
Redistilled water 1000g is formulated, and the mass ratio of NaOH and intercalated graphite in NaOH solution are：mNaOH：mGraphite=1：1,
At a temperature of 60 DEG C, 5min is soaked, is cleaned 3 times using redistilled water, is crushed, is carried out spheroidization processing with balling machine, produce lithium
Ion battery cathode material.
Embodiment 4
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) spheroidization crystalline flake graphite 10g, oxidants hydrogen peroxide 40g, organic acid+benzoic acid 20g are mixed, the spheroidization
The particle diameter D of crystalline flake graphite50=40 μm, phosphorus content is 99.96wt%, at a temperature of 40 DEG C, stirring, reacts 2h, by obtaining for obtaining
Mixture is washed to pH=6.5, is dried at a temperature of 80 DEG C, obtains powders A；
2) powders A is sent into Muffle furnace, 800 DEG C is warming up to 2 DEG C/min heating rate, be incubated 2h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) intercalated graphite made from 1.0g is added in the NaOH solution that concentration is 0.75g/L, the NaOH in NaOH solution
Mass ratio with intercalated graphite is：mNaOH：mGraphite=1：1, at a temperature of 45 DEG C, 25min is soaked, 3 are cleaned using redistilled water
It is secondary, crush, carry out spheroidization processing with balling machine, produce lithium ion battery negative material.
Embodiment 5
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) spheroidization crystalline flake graphite 10g, oxidants hydrogen peroxide 30g, organic acid tartaric acid 10g are mixed, the spheroidization
The particle diameter D of crystalline flake graphite50=35 μm, phosphorus content is 99.96wt%, at a temperature of 30 DEG C, stirring, reacts 4h, by obtaining for obtaining
Mixture is washed to pH=6, is dried at a temperature of 90 DEG C, obtains powders A；
2) powders A is sent into Muffle furnace, 900 DEG C is warming up to 3 DEG C/min heating rate, be incubated 1h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) intercalated graphite made from 1.0g is added into concentration in 0.5g/L NaOH solution, NaOH in NaOH solution with
The mass ratio of intercalated graphite is：mNaOH：mGraphite=1：8, at a temperature of 50 DEG C, 25min is soaked, 3 are cleaned using redistilled water
It is secondary, crush, carry out spheroidization processing with balling machine, produce lithium ion battery negative material.
Embodiment 6
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) spheroidization spherical graphite 10g, oxidant potassium permanganate 50g, organic acid citric acid 30g are mixed, the spheroidization
The particle diameter D of spherical graphite50=30 μm, phosphorus content is 99.96wt%, at a temperature of 40 DEG C, stirring, reacts 2h, by obtaining for obtaining
Mixture is washed to pH=7, is dried at a temperature of 80 DEG C, obtains powders A；
2) powders A is sent into heating furnace, 600 DEG C is warming up to 2 DEG C/min heating rate, be incubated 4h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) intercalated graphite made from 1.0g is added into concentration in 0.5g/L NaOH solution, NaOH in NaOH solution with
The mass ratio of intercalated graphite is：mNaOH：mGraphite=1：5, at a temperature of 30 DEG C, 20min is soaked, 3 are cleaned using redistilled water
It is secondary, crush, carry out spheroidization processing with balling machine, produce lithium ion battery negative material.
Embodiment 7
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
1) spheroidization spherical graphite 10g, oxidant ammonium nitrate 40g, organic acid laurate 20g are mixed, the spheroidization ball
The particle diameter D of shape graphite50=35 μm, phosphorus content is 99.96wt%, at a temperature of 30 DEG C, stirring, reacts 2h, must be mixed what is obtained
Compound is washed to pH=6.5, is dried at a temperature of 80 DEG C, obtains powders A；
2) powders A is sent into Muffle furnace, 600 DEG C is warming up to 1 DEG C/min heating rate, be incubated 3h, furnace cooling
To room temperature, that is, intercalated graphite is made.
3) intercalated graphite made from 1.0g is added into concentration in 1.0g/L NaOH solution, NaOH in NaOH solution with
The mass ratio of intercalated graphite is：mNaOH：mGraphite=1：5, at a temperature of 40 DEG C, 20min is soaked, 3 are cleaned using redistilled water
It is secondary, crush, carry out spheroidization processing with balling machine, produce lithium ion battery negative material.
Embodiment 8
The preparation method of the lithium ion battery negative material of the present embodiment, comprises the following steps：
5g intercalated graphites are added into concentration in 12g/L NaOH solution, the intercalated graphite can be using in the prior art
Intercalated graphite, microdilatancy graphite cathode made from embodiment 2 in background technology (CN104157863A) is used in the present embodiment
The mass ratio of NaOH and intercalated graphite in material, NaOH solution is：mNaOH：mGraphite=1：12, at a temperature of 40 DEG C, immersion
10min, separation, solid is cleaned 3 times using redistilled water, is crushed, is carried out spheroidization processing with balling machine, produce lithium-ion electric
Pond negative material.
Experimental example
From the negative material of commercially available unmodified Delanium as a comparison case, comparative example and embodiment 1-8 are made
Lithium ion battery negative material carry out as follows physically and electrically chemical property test.
(1) pattern test.
Using the pattern of obtained negative material in SEM methods testing example 1, as a result as shown in Figure 1.
(2) button cell test is made.
The lithium ion battery negative material obtained in contrast negative material and embodiment 1-8 is assembled into as follows
Button cell is simultaneously tested：
1) 220mL solvent redistilled waters are added in 95g negative materials, 1g binding agent LA132,4g conductive agents SP, are stirred
Mix and uniformly prepare cathode size, be coated on copper foil, dry, roll pressing obtains negative pole.
Electrolyte uses LiPF6For electrolyte, concentration is 1.3mol/L, and volume ratio is 1:1 EC and DEC is solvent, gold
Belong to lithium piece as to electrode, barrier film uses polyethylene (PE), polypropylene (PP) or poly- second propylene (PEP) composite membrane, is being flushed with hydrogen gas
Glove box according to existing method assemble button cell.Contrast negative material and the lithium ion battery obtained in embodiment 1-8
It is A, A1, A2, A3, A4, A5, A6, A7, A8 that battery made from negative material is numbered respectively.
2) above-mentioned button cell is tested on new prestige 5V/10mA type cell testers, charging/discharging voltage scope 0.005-
2.0V, charge-discharge magnification 0.1C, as shown in table 1, the electric discharge of embodiment 1-3 lithium ion battery negative material is electric for test result
Pressure-specific capacity curve is as shown in Figure 2.
The button cell test result of table 1
| The electric battery of button | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A |
| Discharge capacity (mAh/g) first | 364.1 | 365.4 | 361.8 | 360.8 | 360.3 | 361.1 | 362.8 | 341.5 | 339.5 |
| Efficiency (%) first | 95.1 | 94.8 | 94.3 | 93.9 | 94.1 | 93.9 | 94.3 | 92.8 | 92.4 |
Note：Discharge capacity/initial charge the capacity of efficiency=first first in table.
(3) soft-package battery test is made.
1) it is used as negative pole material to contrast obtained lithium ion battery negative material in negative material and embodiment 1-8 respectively
Material, using LiFePO 4 material as positive electrode, electrolyte uses LiPF6For electrolyte, concentration is 1.3mol/L, and volume ratio is 1:
1 EC and DEC is solvent, and barrier film uses the films of Celgard 2400, and 5Ah soft-package batteries are prepared using prior art, and contrast is negative
Soft-package battery made from lithium ion battery negative material in pole material and embodiment 1-8 number respectively be B, B1, B2, B3, B4,
B5、B6、B7、B8。
2) high rate performance and cycle performance of above-mentioned soft-package battery are tested, wherein high rate performance is tested it and filled in 0.3C respectively
Respectively with the performance of 0.5C, 1.0C, 2.0C, 4.0C, 8.0C multiplying power discharging after electricity, and test its charged with 2.0C, 2.0C electric discharge,
Capability retention after circulating 500 times, as a result as shown in table 2.The multiplying power discharging property curve of B1 soft-package batteries is as shown in figure 3, B
The multiplying power discharging property curve of soft-package battery is as shown in Figure 4.
The soft-package battery test result of table 2
As it can be seen from table 1 using button cell made from the lithium ion battery negative material of the gained of embodiment 1~8, its
Discharge capacity and efficiency are all apparently higher than comparative example, and showing the lithium ion battery negative material of the present invention can be such that battery has well
Discharge capacity and efficiency.From table 2 it can be seen that the high rate performance and cycle performance of the soft-package battery that embodiment 1-8 is prepared
It is substantially better than the soft-package battery of comparative example.
Claims (7)
1. a kind of preparation method of lithium ion battery negative material, it is characterised in that comprise the following steps：
Graphite and oxidant, organic acid reaction are obtained into intercalated graphite, intercalated graphite is added in NaOH solution, is soaked, washing,
Crush, spheroidization processing is produced；The graphite is crystalline flake graphite, ball-type graphite, is handled by spheroidization；The intercalated graphite
Preparation method comprise the following steps：
1) by graphite, oxidant, organic acid with mass ratio 1：(3~5)：(1~3) mix, 0.5- is reacted at a temperature of 20-60 DEG C
4h, obtains mixture washing, drying obtains powders A by what is obtained；
2) powders A is warming up to 600-900 DEG C, is incubated 1-4h, produces.
2. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterised in that the NaOH solution
Concentration is 0.5~1.0g/L.
3. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterised in that the soaking temperature is
20-60℃。
4. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterised in that the soak time is
5-30min。
5. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterised in that the oxidant was
One kind in hydrogen oxide, potassium permanganate, ammonium nitrate.
6. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterised in that the organic acid is second
One kind in diacid, succinic acid, adipic acid, tartaric acid, benzoic acid, citric acid or laurate.
7. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterised in that the step 2) middle liter
The speed of temperature is 1~3 DEG C/min.
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| CN108711623A (en) * | 2018-05-30 | 2018-10-26 | 欣旺达电子股份有限公司 | Lithium ion battery, negative plate, composite graphite negative electrode material and preparation method thereof |
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