CN104934579B - A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material - Google Patents
A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material Download PDFInfo
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 107
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- 238000000576 coating method Methods 0.000 title claims abstract description 24
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of doping of porous graphite and the preparation method of carbon coating graphite cathode material, the modification of porous carbon doping and carbon coating to graphite can solve graphite high rate capability it is poor the problem of, because the porous carbon of doping serves the effect of electric transmission cushion in graphite material, therefore the introducing of the cycle performance and the other carbon material of high magnification charge and discharge point performance that improve graphite material can effectively suppress common embedding effect of the electrolyte to graphite, the anti-organic solvent erosiveness of graphite is improved, the cycle performance of graphite is further improved.
Description
Technical field
The present invention relates to lithium ion battery negative material, and in particular to a kind of porous graphite doping and carbon coating graphite cathode
The preparation method of material.
Background technology
With the development of automobile industry, the exhaustion of the non-renewable fossil fuel such as oil, natural gas is of increasing concern, empty
Gas pollutes and room temperature effect also turns into global problem.To solve energy problem, low-carbon environment-friendly is realized, based on current energy skill
The development level of art, electric vehicle engineering is increasingly becoming the emphasis direction of global economic development, the U.S., Japan, Germany, China etc.
The national fuel vehicle of limitation in succession is used, and greatly develops electric car.It is used as the core component of electric automobile --- electrokinetic cell is also met
Big good opportunity to develop is carried out.Electrokinetic cell refers to the battery applied to electric car, including lithium ion battery, lead-acid battery, combustion
Expect battery etc., wherein, lithium ion battery is because with specific energy is high, specific power is big, self discharge is few, service life length and security are good
The advantages of, it has also become the emphasis of current various countries' development.
Lithium ion battery is as the remarkable new generation of green high-energy battery of performance, and it has, and high voltage, energy density are big, follow
The distinguishing feature such as ring performance is good, self discharge is small, memory-less effect, operating temperature range are wide.Present lithium ion cell electrode material
Expect that positive electrode is mainly LiCoO2、LiNiO2And LiMn2O4Deng.Co systems toxicity is larger, and Ni systems synthesis condition is harsh, Mn systems
Jahn-Teller effect cycle performances are bad.LiFePO4Ratio in lithium ion battery of future generation is acknowledged as to have wide application prospects
One of positive electrode.However, the security of negative pole is then often ignored by people, current lithium ion battery negative material is mainly
Carbon material.
And there is relatively low lithium insertion/deintercalation current potential as the graphite type material of lithium ion battery negative material, it is suitable
Reversible capacity and aboundresources, it is cheap the advantages of, be more satisfactory lithium ion battery negative material.But there is also head for it
Secondary discharging efficiency is low, cycle performance is poor, it is selectively high to electrolyte the shortcomings of, be restricted graphite material application.To understand
The certainly disadvantages mentioned above of graphite material, people are modified processing to graphite by various methods, and the method generally used at present is
Carbon coating method.Yang Ruizhi etc. exists《Resin carbon coated graphite as lithium ion battery negative electrode research》(《Journal of Inorganic Materials》,
2000,15(4)：712-718) with liquid-phase impregnation process in natural flake graphite Surface coating phenolic resin in, filled with constant current,
Electric discharge, powder microelectrode cyclic voltammetry has investigated charging-discharging performances.Test result indicates that, thermally treated phenolic resin carbon
Coated graphite material puts that a capacity is higher, and cycle life is longer, can as high performance lithium ion battery negative material.He Ming
Deng《The preparation of resin carbon-coated graphite and its chemical property》(《Battery》, 2003,3 (5)：281-284) in day in
Right micro crystal graphite particle surface coats one layer of resin carbon, and cladding processing can reduce the appearance irreversible first of natural micro crystal graphite
Amount, using first mixing and then scattered method coated graphite, inside is natural micro crystal graphite, and outside is 1~2 μm of phenolic resin
Pyrolytic carbon layer.The irreversible capacity that lithium ion experimental cell measures natural micro crystal graphite is 14%, the irreversible appearance of coated graphite
Measure as 7%.Cladding processing can largely reduce the irreversible capacity of natural micro crystal graphite.Chen Meng etc. exists《Pitch-coating
The preparation of native graphite and performance study》(《Battery industry》, 2007,12 (5)：298-302) liquid phase coating method is used, will be dripped
Green grass or young crops cracking carbon coating is on natural spherical plumbago, to improve its cycle performance.Test result indicates that, native graphite is through pitch-coating
Afterwards, irreversible capacity loss has been reduced to 32.5mAh/g from 125.5mAh/g, and specific capacity is brought up to from 290.8mAh/g
365.3mAh/g, the capability retention after 50 circulations has brought up to 93.66% from 55.4%, effectively improves native graphite
Cycle performance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of porous graphite doping and carbon coating graphite cathode material
Preparation method, it is therefore intended that the problems such as solving poor graphite high-rate charge-discharge capability and anti-electrolyte organic solvent poor compatibility,
Improve the cycle performance of discharge and recharge.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：A kind of porous graphite doping and carbon coating graphite
The preparation method of negative material, it is characterised in that comprise the following steps：
(1) configuration concentration is 1~12mg/mL potassium permanganate solution, adds graphite and carries out oxidation pore-creating, washing is dried
It is dry, obtain porous graphite；
(2) according to porous graphite：Graphite=(0.02~0.1)：1 ratio, while 5~20% ratio of graphite weight
A certain amount of carbon matrix precursor is added, is well mixed, obtains porous graphite and graphite and carbon matrix precursor composite granule；
(3) under nitrogen protection, the composite granule in step (2) is heated to 700~950 with 2~10 DEG C/min heatings
DEG C, and continue 3~20 hours, cool down to after room temperature, pulverize and sieve, that is, obtain porous graphite doping and carbon coating graphite cathode
Material.
Graphite in step (1) is native graphite, particle diameter D50≤5 μm, specific surface area >=10m2/g。
Graphite in step (2) is Delanium or native graphite, and particle diameter D50 is between 5~25 μm, specific surface area≤6m2/
G, tap density >=0.7g/cm3。
Carbon matrix precursor described in step (2) is sodium cellulose glycolate, polyvinyl alcohol, phenolic resin, epoxy resin, Portugal
Mixture more than one or both of grape sugar, starch, pitch.
Compared with prior art, the advantage of the invention is that porous graphite doping improves the conductance of graphite with carbon coating
Rate, obtained porous graphite doping is high with carbon coating graphite cathode material specific capacity, and good cycle can be widely applied to various
Lithium ion battery.Meanwhile, preparation method of the invention is with low cost, and technique is simple, is suitable for large-scale industrial production.
The problem of high rate capability that porous carbon can solve graphite to the doping vario-property of graphite is poor, it is porous due to doping
Carbon serves the effect of electric transmission cushion in graphite material, therefore improves the cycle performance and high magnification of graphite material
The introducing of the other carbon material of charge and discharge point performance can effectively suppress common embedding effect of the electrolyte to graphite, and raising graphite resists organic molten
Agent erosiveness, further improves the cycle performance of graphite.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material, comprise the following steps：
(1) 5mg/mL potassium permanganate solution is prepared, by 50g native graphite (particle diameter D50：3.63 μm, compare surface
Product：12.51m2/ g) be added in solution, then oxidation processes 60min is washed with water to neutrality, then dry for standby；
(2) according to porous graphite：Graphite (D50：10.82 μm, specific surface area：6.1m2/ g, tap density：0.96g/cm3)
=0.02：1 ratio, while the ratio of graphite weight 5% adds a certain amount of carbon matrix precursor (pitch powder), is well mixed,
Obtain porous graphite and graphite and carbon matrix precursor composite granule；
(3) under nitrogen protection, the composite granule in step (2) is heated to 950 DEG C with 10 DEG C/min heatings, and continued
3 hours, cool down to after room temperature, pulverize and sieve, that is, obtain porous graphite doping and carbon coating graphite cathode material.
Embodiment 2
A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material, comprise the following steps：
(1) 10mg/mL potassium permanganate solution is prepared, by 50g native graphite (particle diameter D50：5.42 μm, compare surface
Product：18.12m2/ g) be added in solution, then oxidation processes 30min is washed with water to neutrality, then dry for standby；
(2) according to porous graphite：Graphite (D50：17.21 μm, specific surface area：5.8m2/ g, tap density：0.85g/cm3)
=0.1：1 ratio, while the ratio of graphite weight 10% adds a certain amount of carbon matrix precursor (phenolic resin powder), mixing is equal
It is even, obtain porous graphite and graphite and carbon matrix precursor composite granule；
(3) under nitrogen protection, the composite granule in step (2) is heated to 900 DEG C with 5 DEG C/min heatings, and continues 5
Hour, cool down to after room temperature, pulverize and sieve, that is, obtain porous graphite doping and carbon coating graphite cathode material.
Embodiment 3
A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material, comprise the following steps：
(1) 8mg/mL potassium permanganate solution is prepared, by 50g native graphite (particle diameter D50：7.28 μm, compare surface
Product：15.42m2/ g) be added in solution, then oxidation processes 50min is washed with water to neutrality, then dry for standby；
(2) according to porous graphite：Graphite (D50：8.14 μm, specific surface area：6.9m2/ g, tap density：1.04g/cm3)=
0.08：1 ratio, while the ratio of graphite weight 7% adds a certain amount of carbon matrix precursor (epoxy resin powder), mixing is equal
It is even, obtain porous graphite and graphite and carbon matrix precursor composite granule；
(3) under nitrogen protection, the composite granule in step (2) is heated to 850 DEG C with 8 DEG C/min heatings, and continues 6
Hour, cool down to after room temperature, pulverize and sieve, that is, obtain porous graphite doping and carbon coating graphite cathode material.
Comparative example 1
Undressed native graphite in embodiment 1.
Comparative example 2
Undressed Delanium in embodiment 2.
Electrochemical property test
The performance of the modification lithium-ion battery graphite cathode material prepared for inspection the inventive method, with half-cell test side
Method is tested, with above example and the negative material of comparative example：Acetylene black：PVDF (Kynoar)=95：2：3 (weights
Amount ratio), plus NMP (1-METHYLPYRROLIDONE) is tuned into pulpous state in right amount, is coated on copper foil, is made within 8 hours through 110 DEG C of dryings of vacuum
Negative plate；Using metal lithium sheet as to electrode, electrolyte is 1mol/L LiPF6/EC+DEC+DMC=1：1：1, microporous polypropylene membrane
For barrier film, battery is assembled into.Charging/discharging voltage is 0~2.0V, and charge-discharge velocity is 0.5C, and energy test is carried out to battery performance,
Test result is shown in Table 1.
Table 1 for negative material in not be the same as Example and comparative example performance comparision
General principle of the present utility model and principal character and advantage of the present utility model, one's own profession has been shown and described above
The technical staff of industry is it should be appreciated that the utility model is not restricted to the described embodiments, described in above-described embodiment and specification
Simply illustrate principle of the present utility model, on the premise of the utility model spirit and scope are not departed from, the utility model is also
Various changes and modifications are had, these changes and improvements are both fallen within the range of claimed the utility model, the utility model
Claimed scope is by appended claims and its equivalent thereof.
Claims (3)
1. a kind of porous graphite doping and the preparation method of carbon coating graphite cathode material, it is characterised in that comprise the following steps：
(1) porous graphite is prepared：Configuration concentration is 1-12mg/mL potassium permanganate solution, adds graphite and carries out oxidation pore-creating,
Washing and drying, obtains porous graphite；
(2) prepared by graphite presoma：According to porous graphite：Graphite=(0.02~0.1)：1 ratio, while the 5 of graphite weight
~20% ratio adds a certain amount of carbon matrix precursor, is well mixed, and obtains porous graphite and graphite and carbon matrix precursor is compound
Powder；
(3) high-temperature process：Under nitrogen protection, the powder of drying in step (2) is heated to 700 with 2~10 DEG C/min heatings
~950 DEG C, and continue 3-20 hours, cool down to after room temperature, pulverize and sieve, that is, obtain porous graphite doping and carbon coating graphite
Negative material.
2. a kind of porous graphite doping according to claim 1 and the preparation method of carbon coating graphite cathode material, it is special
It is native graphite, particle diameter D50≤10 μm, specific surface area >=10m to levy the graphite being in step (1)2Stone in/g, step (2)
Ink is Delanium or native graphite, and particle diameter D50 is between 5~25 μm, specific surface area≤6m2/ g, tap density >=0.7g/cm3。
3. a kind of porous graphite doping according to claim 1 and the preparation method of carbon coating graphite cathode material, it is special
Levy and be that the carbon source presoma described in step (2) is sodium cellulose glycolate, polyvinyl alcohol, phenolic resin, epoxy resin, Portugal
Mixture more than one or both of grape sugar, starch, pitch.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710461064.5A CN107275610A (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of porous graphite doped graphite negative material |
| CN201710461076.8A CN107069015A (en) | 2015-05-22 | 2015-05-22 | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material |
| CN201710461072.XA CN107180962A (en) | 2015-05-22 | 2015-05-22 | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material |
| CN201710461050.3A CN107221661A (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of graphite negative material of lithium ion battery |
| CN201710461071.5A CN107069014A (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of graphite negative material of lithium ion battery |
| CN201510266046.2A CN104934579B (en) | 2015-05-22 | 2015-05-22 | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510266046.2A CN104934579B (en) | 2015-05-22 | 2015-05-22 | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material |
Related Child Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710461050.3A Division CN107221661A (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of graphite negative material of lithium ion battery |
| CN201710461076.8A Division CN107069015A (en) | 2015-05-22 | 2015-05-22 | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material |
| CN201710461072.XA Division CN107180962A (en) | 2015-05-22 | 2015-05-22 | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material |
| CN201710461064.5A Division CN107275610A (en) | 2015-05-22 | 2015-05-22 | A kind of preparation method of porous graphite doped graphite negative material |
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| CN107611445A (en) * | 2017-09-18 | 2018-01-19 | 华南师范大学 | A kind of preparation method of lithium ion battery graphite cathode material |
| CN108417800B (en) * | 2018-03-07 | 2021-01-12 | 深圳市本征方程石墨烯技术股份有限公司 | Graphene-coated graphite/metal composite powder negative electrode material and preparation method thereof |
| CN109546099B (en) * | 2018-10-16 | 2021-08-31 | 中航锂电（洛阳）有限公司 | Graphite composite negative electrode material, preparation method thereof and lithium ion battery |
| CN109850886B (en) * | 2019-01-18 | 2022-07-26 | 华南理工大学 | Porous graphite material and preparation method and application thereof |
| CN110165179B (en) * | 2019-05-24 | 2022-07-08 | 广西安德丰新能源有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery containing negative electrode material |
| CN114477160B (en) * | 2020-10-27 | 2023-07-18 | 武汉大学 | Method for preparing high-purity porous graphite |
| CN114520314B (en) * | 2020-11-19 | 2024-02-27 | 湖南中科星城石墨有限公司 | Negative electrode material with porous carbon coating layer, preparation method thereof and lithium ion battery |
| CN113113600A (en) * | 2021-04-06 | 2021-07-13 | 常德速碳新能源科技有限公司 | Negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN112952069A (en) * | 2021-04-06 | 2021-06-11 | 黑龙江省宝泉岭农垦溢祥新能源材料有限公司 | Production process of carbon-coated graphite negative electrode material |
| CN112952070A (en) * | 2021-04-08 | 2021-06-11 | 黑龙江省宝泉岭农垦溢祥新能源材料有限公司 | Graphite lithium battery negative electrode material and preparation method thereof |
| CN114188533B (en) * | 2021-12-20 | 2023-06-30 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
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| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| CN102769139A (en) * | 2012-08-10 | 2012-11-07 | 深圳市斯诺实业发展有限公司永丰县分公司 | Preparation method of high power capacity lithium ion battery cathode material |
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