CN105845886A - Negative electrode material for ion battery and preparation method of negative electrode material - Google Patents
Negative electrode material for ion battery and preparation method of negative electrode material Download PDFInfo
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- CN105845886A CN105845886A CN201610338632.8A CN201610338632A CN105845886A CN 105845886 A CN105845886 A CN 105845886A CN 201610338632 A CN201610338632 A CN 201610338632A CN 105845886 A CN105845886 A CN 105845886A
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- ion battery
- coke
- negative electrode
- electrode material
- coke powder
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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
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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
-
- 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 invention relates to a negative electrode material for an ion battery and a preparation method of the negative electrode material. The negative electrode material for the ion battery comprises powdery coke powder and a water-soluble high-molecular polymer, wherein the coke powder is green coke and comprises one or more of needle coke, petroleum coke or pitch coke; and the preparation method of the negative electrode material comprises the following steps: mixing a mixture of one or more of the coke powder with a water solution of the water-soluble high-molecular polymer evenly at a certain ratio, separating the coke powder from water, drying the coke powder, carrying out low-temperature carbonization under inert gas protection, and then carrying out high-temperature graphitizing treatment. By negative electrode material for the ion battery, the capacity play performance of the graphitic negative electrode material at a low temperature is improved; and the cycling stability is improved. Un-graphitized green coke powder is utilized as the raw material, and graphitization is carried out after coating, so that the secondary graphitization process on artificial graphite is avoided; and the production cost is greatly reduced.
Description
Technical field
The present invention relates to cell art, especially relate to a kind of ion battery cathode material and preparation method thereof.
Background technology
At present, lithium ion battery has been widely used for various field as the environmental protection energy.Lithium ion battery has that energy density is high, specific power big, good cycle.Memory-less effect, the feature such as pollution-free.But poor cryogenic property makes its application be restricted.Lithium ion battery negative material has native graphite, Delanium and a few class of alloy type material, and wherein graphite type material is because having the advantages such as capacity height, low, the good cycling stability of intercalation potential, and is widely used.Research think that negative pole poor performance at low temperatures is because what lithium ion diffusion velocity under cryogenic caused slowly, temperature is the lowest, and the diffusion of lithium ion is the most difficult, the easiest negative terminal surface separate out with deposition lithium metal.
Patent JP2009-117334 finds low-crystalline carbon to be coated on anisotropic graphite particle surface and can improve charging load performance, but this method is relatively big because of the irreversible capacity of low-crystalline carbon self, causes just recharging discharging efficiency low.And because low-crystalline carbon particle is harder, difficulty stripping electrode after compacting, the advantage therefore losing anisotropic graphite particle, the performance of lithium-ion secondary battery produced is low.Simultaneously as currently used be Delanium cladding after, then graphitizing method, cause product needed to carry out secondary graphitizing, product cost remains high.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of ion battery cathode material and preparation method thereof, (capacity performance rate=first capacity/actual capacity * 100%) and the problem of capacity attenuation improving graphite negative electrodes material capacity at low temperatures and play.
The technical scheme that the present invention provides is as follows:
A kind of lithium ion battery negative material, including coke powder and the high molecular weight water soluble polymer of powdery, described coke powder is green coke, including one or more of needle coke, petroleum coke or pitch coke；Described high molecular weight water soluble polymer proportion in cell negative electrode material is 0.1-50%.
The mean diameter of described coke powder is 8-40 μm, specific surface area≤5.0m2/g。
A kind of preparation method preparing described lithium ion battery negative material, step is as follows:
The mixture of one or more of described coke powder is uniform with the aqueous solution of high molecular weight water soluble polymer according to a certain percentage, make coke powder be separated from water afterwards and under inert gas shielding, carry out low-temperature carbonization after drying, carry out high temperature graphitization process the most again.
Described high molecular weight water soluble polymer is a kind of in polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyethylene Glycol or carboxymethyl cellulose.
In the aqueous solution of described high molecular weight water soluble polymer, the ratio of high molecular weight water soluble polymer and water is 1:0.5-10, and described water is deionized water.
The temperature of described low-temperature carbonization is 600-1500 DEG C, and temperature retention time is 4-48 hour；The temperature that described high temperature graphitization processes is 2500-3200 DEG C, and temperature retention time is 24-72 hour.
Described noble gas is the gaseous mixture of two or three in argon, helium, neon, nitrogen.
Invention increases graphite negative electrodes material capacity at low temperatures and play performance, improve cyclical stability, be raw material owing to using the most graphited coking powder, after cladding, carry out graphitization, avoid Delanium and carry out the technique of secondary graphitizing, greatly reduce production cost.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph of lithium ion battery negative material prepared by the present invention.
Detailed description of the invention
Below, in conjunction with example, substantive distinguishing features and the advantage of the present invention are further described, but the invention is not limited in listed embodiment.
Embodiment 1:
2L reactor adds 1.5L deionized water, rotating speed 110r/min, add 500g polyacrylamide while stirring, polyacrylamide adds 1500g petroleum coke coking powder (D50=20.532 μm after being completely dissolved, specific surface area 4.136m2/g), stir 3h, mixture is centrifuged 150 DEG C of dry 4h, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample A.
Embodiment 2:
2L reactor adds 1.5L deionized water, rotating speed 110r/min, add 250g polyacrylamide while stirring, polyacrylamide adds 2000g petroleum coke coking powder (D50=18.495 μm after being completely dissolved, specific surface area 3.580m2/g), stir 3h, mixture is centrifuged 150 DEG C of dry 4h, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample B.
Embodiment 3:
2L reactor adds 1.5L deionized water, rotating speed 110r/min, add 300g polyacrylic acid while stirring, polyacrylic acid adds 1500g Raw needle coke powder (D50:15.851 μm after being completely dissolved, specific surface area 3.968m2/g), stir 2h, mixture is spray-dried, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample C.
Embodiment 4:
2L reactor adds 1.5L deionized water, rotating speed 110r/min, add 200g Polyethylene Glycol while stirring, Polyethylene Glycol adds 1000g Raw needle coke powder (D50:15.160 μm after being completely dissolved, specific surface area 3.344m2/g), stir 4h, mixture is spray-dried, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample D.
Embodiment 5:
2L reactor adds 1.5L deionized water, rotating speed 110r/min, add 150g carboxymethyl cellulose while stirring, carboxymethyl cellulose adds 1500g pitch coke coking powder (D50:25.508 μm after being completely dissolved, specific surface area 2.459m2/g), stir 4h, mixture is spray-dried, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample E.
Embodiment 6:
2L reactor adds 1.5L deionized water, rotating speed 110r/min, add 200g polyvinyl alcohol while stirring, polyvinyl alcohol adds 1500g Raw needle coke powder (D50:13.962 μm after being completely dissolved, specific surface area 4.768m2/g), stir 3h, mixture is centrifuged 150 DEG C and is dried, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample F.
Comparative example:
Using D50:13.962 μm, the Raw needle coke powder of specific surface area 4.768m2/g, 1200 DEG C of low-temperature carbonizations, 2800 DEG C of graphitizations obtain sample G.
Make 18650 cylindrical batteries (capacity 2000mAh) test sample A as follows, B, C, D, E, F, G play and cycle performance at low temperature-10 DEG C, the 1C charge and discharge capacity of 100 weeks.
The making of positive pole:
Kynoar (PVDF) is dissolved in N-first class ketopyrrolidine (NMP), makes glue, then by LiCoO2Add in above-mentioned glue with the mixed-powder of acetylene black, mixing, make slurry, wherein LiCoO2: acetylene black: PVDF=93:3:4.Then slurry is applied uniformly with on the aluminium foil of 13 μm, vacuum tank 100 DEG C drying, roll.
The making of negative pole:
Kynoar (PVDF) is dissolved in N-first class ketopyrrolidine (NMP), make 12% (weight/mass percentage composition) glue, then active substance (A-G) and SP are added above-mentioned glue, active substance: SP:PVDF=94:2:4, on slurry even application and 10 μm Copper Foils, vacuum tank 70-130 DEG C drying, rolls.
The configuration of electrolyte: mixed with 1:1 by EC with DEC routinely, adds a small amount of typical additives, then by LiPF simultaneously6It is dissolved in wherein, makes the electrolyte that concentration is 1mol/L；
The making of battery: above-mentioned positive and negative plate is wound together with the polypropylene micropore diaphragm of 20 μ m-thick making 18650 cylindrical batteries.Carry out performance test at-10 DEG C, obtain test result such as table 1 below:
Table 1
It can be seen that use the battery of the making of the present invention to be respectively provided with higher advantage in terms of capacity performance rate with capability retention.
Above invention is described in detail, but described content has been only the preferred embodiment of invention, it is impossible to be considered the practical range for limiting invention.All impartial changes made according to patent application scope and improvement etc., within all should still belonging to the patent covering scope of invention.
Claims (8)
1. a lithium ion battery negative material, it is characterised in that include coke powder and the high molecular weight water soluble polymer of powdery,
Described coke powder is green coke, including one or more of needle coke, petroleum coke or pitch coke；Described water soluble polymer is polymerized
Thing proportion in cell negative electrode material is 0.1-50%.
Lithium ion battery negative material the most according to claim 1, it is characterised in that the mean diameter of described coke powder is
8-40 μm, specific surface area≤5.0m2/g。
Lithium ion battery negative material the most according to claim 1, it is characterised in that described water soluble polymer gathers
Compound is a kind of in polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyethylene Glycol or carboxymethyl cellulose.
4. preparing a preparation method for lithium ion battery negative material described in any one of claim 1-3, its feature exists
In, step is as follows:
By the mixture of one or more of described coke powder according to a certain percentage with the aqueous solution of high molecular weight water soluble polymer
Mix homogeneously, makes coke powder be separated from water afterwards and carries out low-temperature carbonization under inert gas shielding after drying, carry out height the most again
Temperature graphitization processing.
The preparation method of lithium ion battery negative material the most according to claim 4, it is characterised in that described water solublity
High molecular polymer is a kind of in polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyethylene Glycol or carboxymethyl cellulose.
The preparation method of lithium ion battery negative material the most according to claim 5, it is characterised in that described water solublity
In the aqueous solution of high molecular polymer, the ratio of high molecular weight water soluble polymer and water is 1:0.5-10, and described water is deionization
Water.
The preparation method of lithium ion battery negative material the most according to claim 6, it is characterised in that described low temperature charcoal
The temperature changed is 600-1500 DEG C, and temperature retention time is 4-48 hour；The temperature that described high temperature graphitization processes is
2500-3200 DEG C, temperature retention time is 24-72 hour.
8. according to the preparation method of lithium ion battery negative material described in any one of claim 4-7, it is characterised in that institute
State noble gas be in argon, helium, neon, nitrogen two or three gaseous mixture.
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| CN201610338632.8A CN105845886A (en) | 2016-05-19 | 2016-05-19 | Negative electrode material for ion battery and preparation method of negative electrode material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887593A (en) * | 2017-03-23 | 2017-06-23 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of cathode material for high capacity lithium ion battery |
| CN108550850A (en) * | 2018-05-08 | 2018-09-18 | 中航锂电（洛阳）有限公司 | A kind of high power capacity high-pressure solid artificial plumbago negative pole material and preparation method thereof, lithium ion battery |
| CN110718690A (en) * | 2018-07-12 | 2020-01-21 | 宝武炭材料科技有限公司 | Preparation method of battery negative electrode material based on needle coke green coke and calcined coke |
| CN113258063A (en) * | 2021-04-29 | 2021-08-13 | 河南易成瀚博能源科技有限公司 | Method for preparing graphite cathode material of lithium ion battery by spray drying method |
| WO2022121136A1 (en) * | 2020-12-10 | 2022-06-16 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material for high-rate lithium ion battery and preparation method therefor |
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| CN1496588A (en) * | 2001-03-06 | 2004-05-12 | ������ѧ��ʽ���� | Graphite material for negative pole of lithium secondary battery, method of manufacturing graphite material, and lithium secondary battery |
| CN101908627A (en) * | 2010-08-05 | 2010-12-08 | 吴壮雄 | Cathode material of lithium ion secondary battery and preparation method thereof |
| CN105280918A (en) * | 2014-10-27 | 2016-01-27 | 湖南摩根海容新材料有限责任公司 | Preparation method of isotropic graphite material |
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2016
- 2016-05-19 CN CN201610338632.8A patent/CN105845886A/en active Pending
Patent Citations (3)
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| CN1496588A (en) * | 2001-03-06 | 2004-05-12 | ������ѧ��ʽ���� | Graphite material for negative pole of lithium secondary battery, method of manufacturing graphite material, and lithium secondary battery |
| CN101908627A (en) * | 2010-08-05 | 2010-12-08 | 吴壮雄 | Cathode material of lithium ion secondary battery and preparation method thereof |
| CN105280918A (en) * | 2014-10-27 | 2016-01-27 | 湖南摩根海容新材料有限责任公司 | Preparation method of isotropic graphite material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887593A (en) * | 2017-03-23 | 2017-06-23 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of cathode material for high capacity lithium ion battery |
| CN106887593B (en) * | 2017-03-23 | 2022-07-29 | 广东天劲新能源科技股份有限公司 | Preparation method of high-capacity lithium ion battery cathode material |
| CN108550850A (en) * | 2018-05-08 | 2018-09-18 | 中航锂电（洛阳）有限公司 | A kind of high power capacity high-pressure solid artificial plumbago negative pole material and preparation method thereof, lithium ion battery |
| CN110718690A (en) * | 2018-07-12 | 2020-01-21 | 宝武炭材料科技有限公司 | Preparation method of battery negative electrode material based on needle coke green coke and calcined coke |
| CN110718690B (en) * | 2018-07-12 | 2022-07-12 | 宝武碳业科技股份有限公司 | Preparation method of battery negative electrode material based on needle coke green coke and calcined coke |
| WO2022121136A1 (en) * | 2020-12-10 | 2022-06-16 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material for high-rate lithium ion battery and preparation method therefor |
| CN113258063A (en) * | 2021-04-29 | 2021-08-13 | 河南易成瀚博能源科技有限公司 | Method for preparing graphite cathode material of lithium ion battery by spray drying method |
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Application publication date: 20160810 |