CN106410197B - A kind of preparation method of graphite cathode material used in lithium ion battery - Google Patents
A kind of preparation method of graphite cathode material used in lithium ion battery Download PDFInfo
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- CN106410197B CN106410197B CN201610322030.3A CN201610322030A CN106410197B CN 106410197 B CN106410197 B CN 106410197B CN 201610322030 A CN201610322030 A CN 201610322030A CN 106410197 B CN106410197 B CN 106410197B
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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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
A kind of preparation method of graphite cathode material used in lithium ion battery, it is prepared including conductive sol solution, the preparation of graphite colloids composite material and porous graphite negative electrode material prepare three processes, it is used in conducting resinl solution preparation process and arrives aqueous solvent, combined conductive agent and binder, it is used in graphite colloids composite material preparation process to graphite and conductive sol solution, it is used in porous graphite negative electrode material preparation process and arrives graphite colloids composite material, activating agent and secondary distilled water, the present invention is good in one layer of conductivity of Graphite Coating, easily-activated conducting resinl, so that active carbon activation is generated the lesser nano-pore in aperture by activation later and leave the biggish um porous in aperture with binder decomposition in conducting resinl, the nanoporous generates synergistic effect in lithium ion battery, the graphite cathode material prepared is set to have imbibition liquid-keeping property strong, compacting The features such as density is high, conductivity is high and its cycle performance is good.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, graphite cathode used in especially a kind of lithium ion battery
The preparation method of material.
Background technique
Negative electrode material is the chief component of lithium ion battery, and the superiority and inferiority of performance influences the circulation of lithium ion battery
Performance, high rate performance and consistency.
Negative electrode material used mainly passes through the coated graphites such as pitch, petroleum coke, phenolic resin and forms currently on the market,
Although having large specific surface area, imbibition ability, cladding consistency and conductivity are poor, influence further mentioning for its performance
It rises.
A series of mistakes such as Chinese patent CN102169988 A mixed with pitch by graphite, cross-linking reaction, high-temperature oxydation
Journey can prepare the composite graphite material with porous structure carbon material clad, although the composite graphite material is in a gram appearance
Amount is played, is promoted in terms of first charge discharge efficiency, but that there are compacted densities is low, conductivity is poor and consistency is more difficult for porous structure
The defects of control.
Summary of the invention
To solve the above problems, the present invention provides a kind of preparation method of graphite cathode material used in lithium ion battery,
By the preparation method, can to prepare that specific surface area is suitable, conductivity is strong, compacted density is high, cycle performance is excellent porous changes
Property graphite cathode material.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of preparation method of graphite cathode material used in lithium ion battery, the preparation method include conductive sol solution system
Standby, graphite colloids composite material preparation and porous graphite negative electrode material prepare three processes, use in conducting resinl solution preparation process
To aqueous solvent, combined conductive agent and binder, using to graphite and conductive peptization in graphite colloids composite material preparation process
Liquid, using arriving graphite colloids composite material, activating agent and secondary distilled water, feature in porous graphite negative electrode material preparation process
It is:
1. conductive sol solution preparation:
The LAl32 of the aqueous solvent of 100 parts by weight, the combined conductive agent of 1~10 parts by weight and 5~8 parts by weight is bonded
Agent, which is mixed and stirred 2~3 hours, prepares conductive sol solution；
Above-mentioned aqueous solvent is deionized water；
Above-mentioned combined conductive agent is made of carbon nanotube and active carbon, and weight ratio is: carbon nanotube: active carbon=1: [1
~10]；
2. prepared by graphite colloids composite material:
By 10~15 parts by weight and granularity is added in the conductive sol solution 1. prepared and is put into togerther for 50 μm of graphite
Disperse 2~12 hours in high speed disperser, prepares graphite colloids composite material；
3. prepared by porous graphite negative electrode material:
The raw material weight configuration proportion for preparing porous graphite negative electrode material is: graphite colloids composite material: activating agent: secondary
Distilled water=1: [1~4]: [10~100]；
Above-mentioned activating agent is any one of KOH, NaOH；
According to above-mentioned weight configuration proportion, graphite colloids composite material and activating agent are put into secondary distilled water and impregnate 4
~6 hours and it is configured to saturated solution, later moves on to the saturated solution in carbide furnace and in N2It is activated under protection, first
Constant temperature is dehydrated 20~40min when rising to 300~500 DEG C with the heating rate of 4 DEG C/min, then activation 60 when being warming up to 850 DEG C~
100min, later in N2Room temperature is cooled to the furnace under protection, can prepare porous graphite negative electrode material.
Due to using technical solution as described above, the present invention generates following good effect:
1, since carbon nanotube conductivity with higher and stronger braced frame act on, can reduce activation,
The structural collapse of oxidation process Hole, and there is the active carbon compared with Large ratio surface to be then easier to live under activating agent use condition
Change and generates nanoporous.
2, in the present invention, due to the carbon nanotube high containing conductivity in conducting resinl, mechanical property is strong, stone can be improved
The conductivity of black negative electrode material, while carbon nanotube can play the role of skeletal support and therefore improve the knot of graphite cathode material
Structure stability and high rate performance, simultaneously because active carbon has biggish specific surface area, the imbibition to graphite cathode material is improved
Liquid-keeping property and cyclicity all have certain effect.
3, the activator such as KOH or NaOH that the present invention uses activate graphite colloids composite material, can increase
The specific surface area of graphite cathode material, make graphite cathode material aperture rationally, stable structure.
Detailed description of the invention
Fig. 1 is the sem test SEM figure of embodiment 1；
Specific embodiment
The present invention is a kind of preparation method of graphite cathode material used in lithium ion battery, and the preparation method is in graphite surface
One layer of good, easily-activated conducting resinl of conductivity is coated, so that active carbon activation is generated the lesser nano-pore in aperture by activation later
And the biggish um porous in aperture is left with binder decomposition in conducting resinl, which generates collaboration in lithium ion battery
Effect, having the graphite cathode material prepared, imbibition liquid-keeping property is strong, compacted density is high, conductivity is high and its cycle performance
The features such as good, therefore the present invention can be described as one kind and prepare graphite cathode material by boring technique.
Preparation method of the invention includes conductive sol solution preparation, the preparation of graphite colloids composite material and porous graphite cathode
Material prepares three processes, uses in conducting resinl solution preparation process and arrives aqueous solvent, combined conductive agent and binder, graphite colloids
Using graphite and conductive sol solution is arrived in composite material preparation process, is used in porous graphite negative electrode material preparation process and arrive graphite
Colloid composite material, activating agent and secondary distilled water, aqueous solvent are deionized waters, and combined conductive agent is by carbon nanotube and activity
Charcoal composition, binder LAl32, graphite or natural graphite or artificial graphite, activating agent are any in KOH, NaOH
Kind.
Following three embodiment is enumerated according to the technical solution.
Embodiment 1:
6 grams of LAl32 binders, 1 gram of carbon nanotube, 9 grams of active carbons and 100 grams of deionized waters are weighed to mix and stir
It mixes 2 hours and prepares into conductive sol solution.The graphite that 15 gram particle degree are 50 μm is added in conductive sol solution and is put into togerther
Disperse 10 hours in high speed disperser, prepares graphite colloids composite material.By 100 grams of graphite colloids composite materials and 300 grams
KOH, which is put into, to be impregnated 5 hours in 1500 grams of secondary distilled waters and is configured to saturated solution, and the saturated solution is moved on to carbide furnace later
In and in N2It is activated, constant temperature dehydration 30min when first rising to 400 DEG C with the heating rate of 4 DEG C/min, then is warming up under protection
80min is activated at 850 DEG C, later in N2Room temperature is cooled to the furnace under protection, can prepare graphite cathode material.
Embodiment 2:
8 grams of LAl32 binders, 2 grams of carbon nanotubes, 8 grams of active carbons and 100 grams of deionized waters are weighed to mix and stir
It mixes 3 hours and prepares into conductive sol solution.The graphite that 13 gram particle degree are 50 μm is added in conductive sol solution and is put into togerther
Disperse 12 hours in high speed disperser, prepares graphite colloids composite material.By 100 grams of graphite colloids composite materials and 400 grams
NaOH, which is put into, to be impregnated 6 hours in 10000 grams of secondary distilled waters and is configured to saturated solution, and the saturated solution is moved on to carbonization later
In furnace and in N2It is activated, constant temperature dehydration 40min when first rising to 300 DEG C with the heating rate of 4 DEG C/min, then is heated up under protection
100min is activated when to 850 DEG C, later in N2Room temperature is cooled to the furnace under protection, can prepare graphite cathode material.
Embodiment 3:
5 grams of LAl32 binders, 1 gram of carbon nanotube, 1 gram of active carbon and 100 grams of deionized waters are weighed to mix and stir
It mixes 3 hours and prepares into conductive sol solution.The graphite that 10 gram particle degree are 50 μm is added in conductive sol solution and is put into togerther
Disperse 12 hours in high speed disperser, prepares graphite colloids composite material.By 100 grams of graphite colloids composite materials and 100 grams
KOH, which is put into, to be impregnated 6 hours in 1000 grams of secondary distilled waters and is configured to saturated solution, and the saturated solution is moved on to carbide furnace later
In and in N2It is activated, constant temperature dehydration 20min when first rising to 500 DEG C with the heating rate of 4 DEG C/min, then is warming up under protection
60min is activated at 850 DEG C, later in N2Room temperature is cooled to the furnace under protection, can prepare graphite cathode material.
Fig. 1 is the sem test SEM figure of embodiment 1, and the sem test SEM figure of embodiment 2-3 is close with Fig. 1
Seemingly, it does not provide separately.
Electrochemical property test:
Respectively using the graphite material that embodiment 1-3 is prepared as lithium ion battery negative material, it is positive with LiFePO4
Pole material, using LiPF6/ EC+DEC [volume ratio is 1: 1] is electrolyte, and 2400 film of Celgard is diaphragm, and correspondence is prepared
5AH soft-package battery A1, A2, A3.
For control cell using artificial graphite as negative electrode material, other conditions ibid prepare 5AH soft-package battery B.
According to national standards in GB/T 24533-2009 " silicon/carbon/graphite in lithium ion batteries class negative electrode material " method test A1,
A2, A3 and B, rate of liquid aspiration and the test reference result for protecting liquid rate see the table below.
| Rate of liquid aspiration (mL/min) | It protects liquid rate (electrolyte content/0h electrolyte content for 24 hours) | |
| A1 | 4.8 | 95.1% |
| A2 | 4.6 | 94.3% |
| A3 | 4.5 | 94.2% |
| B | 3.2 | 83.1% |
| Conductivity (s/m) | |
| A1 | 14.82 |
| A2 | 14.23 |
| A3 | 14.21 |
| B | 7.52 |
Similarly, each capacity retention ratio test reference result of A1, A2, A3 and B see the table below.
From above-mentioned each table and Fig. 1, it is apparent that the graphite cathode material prepared using boring technique of the present invention its
The indices such as rate of liquid aspiration and guarantor's liquid rate obtain different degrees of raising, the lithium ion prepared using graphite cathode material
Its cycle performance of battery is also improved significantly.
Claims (1)
1. a kind of preparation method of graphite cathode material used in lithium ion battery, the preparation method include conductive sol solution preparation,
The preparation of graphite colloids composite material and porous graphite negative electrode material prepare three processes, use in conducting resinl solution preparation process and arrive water
Property solvent, combined conductive agent and binder, using arriving graphite and conducting resinl, porous stone in graphite colloids composite material preparation process
It is used in black negative electrode material preparation process and arrives graphite colloids composite material, activating agent and secondary distilled water, it is characterized in that:
1. conductive sol solution preparation:
The LA132 binder of the aqueous solvent of 100 parts by weight, the combined conductive agent of 1~10 parts by weight and 5~8 parts by weight is mixed
It is combined and stirs 2~3 hours and prepare conductive sol solution；
Above-mentioned aqueous solvent is deionized water；
Above-mentioned combined conductive agent is made of carbon nanotube and active carbon, and weight ratio is: carbon nanotube: active carbon=1: [1~
10]；
2. prepared by graphite colloids composite material:
By 10~15 parts by weight and granularity is added in the conductive sol solution 1. prepared for 50 μm of graphite and is put into togerther high speed
Disperse 2~12 hours in dispersion machine, prepares graphite colloids composite material；
3. prepared by porous graphite negative electrode material:
The raw material weight configuration proportion for preparing porous graphite negative electrode material is: graphite colloids composite material: activating agent: second distillation
Water=1: [1~4]: [10~100]；
Above-mentioned activating agent is any one of KOH, NaOH；
According to above-mentioned weight configuration proportion, it is small that graphite colloids composite material and activating agent are put into immersion 4~6 in secondary distilled water
When and be configured to saturated solution, the saturated solution is moved on in carbide furnace and in N later2It is activated under protection, first with 4
DEG C/heating rate of min when rising to 300~500 DEG C constant temperature be dehydrated 20~40min, then activation 60 when being warming up to 850 DEG C~
100min, later in N2Room temperature is cooled to the furnace under protection, can prepare porous graphite negative electrode material.
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| CN201610322030.3A CN106410197B (en) | 2016-05-17 | 2016-05-17 | A kind of preparation method of graphite cathode material used in lithium ion battery |
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| CN106410197B true CN106410197B (en) | 2019-02-01 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355150A (en) * | 2008-09-03 | 2009-01-28 | 西北大学 | Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery |
| CN101764219A (en) * | 2008-12-24 | 2010-06-30 | 中国科学院金属研究所 | Cathode materials for carbon nano-tube composite lithium ion battery and preparation method thereof |
| CN102169988A (en) * | 2011-03-30 | 2011-08-31 | 深圳市翔丰华科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103247802A (en) * | 2013-05-03 | 2013-08-14 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite composite negative electrode material for lithium ion battery, preparation method of material, and lithium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9853292B2 (en) * | 2009-05-11 | 2017-12-26 | Nexeon Limited | Electrode composition for a secondary battery cell |
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- 2016-05-17 CN CN201610322030.3A patent/CN106410197B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355150A (en) * | 2008-09-03 | 2009-01-28 | 西北大学 | Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery |
| CN101764219A (en) * | 2008-12-24 | 2010-06-30 | 中国科学院金属研究所 | Cathode materials for carbon nano-tube composite lithium ion battery and preparation method thereof |
| CN102169988A (en) * | 2011-03-30 | 2011-08-31 | 深圳市翔丰华科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103247802A (en) * | 2013-05-03 | 2013-08-14 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite composite negative electrode material for lithium ion battery, preparation method of material, and lithium ion battery |
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Effective date of registration: 20180703 Address after: 471000 Kaiyuan County, Kaiyuan Road, Luolong District, Luoyang, Henan Applicant after: Zhao Xiaofeng Address before: 476400 Shangqiu, Henan, Xiayi County Station Town Chen Wa village south Liu Bai Road West Applicant before: HENAN RURAL AMPEREX TECHNOLOGY CO., LTD. |
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Effective date of registration: 20181213 Address after: 336400 Yongfeng Road, Wuliling Industrial Park, Shanggao County, Yichun City, Jiangxi Province Applicant after: Jiangxi Hongcarbon Technology Co., Ltd. Address before: 471000 Kaiyuan County, Kaiyuan Road, Luolong District, Luoyang, Henan Applicant before: Zhao Xiaofeng |
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Effective date of registration: 20190402 Address after: 336400 Wuli Ling Functional Zone of Shanggao County Industrial Park, Yichun City, Jiangxi Province Patentee after: Jiangxi Jiaye Lithium Battery New Energy Technology Co., Ltd. Address before: 336400 Yongfeng Road, Wuliling Industrial Park, Shanggao County, Yichun City, Jiangxi Province Patentee before: Jiangxi Hongcarbon Technology Co., Ltd. |