CN102931413A - Lithium ion battery cathode material - Google Patents
Lithium ion battery cathode material Download PDFInfo
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- CN102931413A CN102931413A CN2012104641496A CN201210464149A CN102931413A CN 102931413 A CN102931413 A CN 102931413A CN 2012104641496 A CN2012104641496 A CN 2012104641496A CN 201210464149 A CN201210464149 A CN 201210464149A CN 102931413 A CN102931413 A CN 102931413A
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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 invention relates to a lithium ion battery cathode material which comprises a silica-based material, wherein a carbon material and a precursor of carbon are coated on the surface of the silica-based material. The lithium ion battery cathode material is characterized in that a lithium salt additive is coated on the surface of the silica-based material; and the mass ratio of the silica-based material to the carbon material to the precursor of carbon to the lithium salt additive is (5-10):(5-10):(15-30):(1-2). Not only is the surface of the silica-based material coated with the carbon material and the precursor of carbon, but also the lithium salt additive is added into the clad material; the coating of materials are improved to a large extent, and the tap density of the materials is effectively improved, and thus the energy density of a lithium ion battery is effectively increased.
Description
Technical field
The invention belongs to the lithium battery material technical field, particularly relate to a kind of lithium ion battery negative material.
Background technology
From the nineties in last century, Sony company uses lamella graphite to replace the metal Li of fail safe extreme difference, be successfully prepared since the lithium rechargeable battery that the first can fill, lithium ion battery is because of its high-energy-density, pollution-free, range of application has obtained develop rapidly, has expanded the fields such as electric tool, electric automobile to from mobile communication power supply, notebook computer, video camera etc.And the electrochemistry capacitance of existing carbon negative pole is on the low side, can not satisfy the further requirement to the portable secondary battery performance of development in science and technology.Silicon materials are because its electrochemical reversible capacity is high, and fail safe is good, and the advantages such as aboundresources have become the preferred material of ion secondary battery cathode material lithium.Silicon materials as lithium ion battery have high theoretical electrochemistry capacity, but the change in volume of silicon materials in the Electrochemical lithiation process is excessive, and first charge-discharge efficiency is lower, seriously hinders the practical application of this electrode material.
At present, usually adopt magnetron sputtering, chemical vapour deposition (CVD), thermal evaporation method prepares the silicon nano thin-film, nano silicon particles, silicon nanowires has been realized the nanocrystallization technology of silicon materials, reduce the internal stress of silicon materials in the Electrochemical lithiation course of reaction and changed, improved first charge-discharge efficiency and cyclical stability.But adopt said method not only to improve the cost of manufacture of cell negative electrode material, and have the low problem of coating weak effect, jolt ramming and compacted density of silica-base material, be not suitable for the needs that large-scale commercial applications is used.
Summary of the invention
The cell negative electrode material cost of manufacture is low, the coating of silica-base material is effective, tap density is high for the technical problem that exists in the solution known technology provides in the present invention, energy density that can the Effective Raise lithium ion battery, and a kind of lithium ion battery negative material of using of suitable large-scale commercial applications.
The technical scheme that the present invention takes is:
A kind of lithium ion battery negative material comprises silica-base material, and the silica-base material surface is coated with the presoma of material with carbon element and carbon, is characterized in: described silica-base material surface is coated with lithium carbonate.
The present invention can also adopt following technical scheme:
The mass ratio that the presoma of described silica-base material, material with carbon element, carbon and lithium carbonate mix is 5-10:5-10:15-30:1-2.
Described silica-base material is polysilicon, monocrystalline silicon, or its mixture; Described material with carbon element is a kind of in Delanium, native graphite, carbon fiber, hard carbon, the agraphitic carbon; The presoma of described carbon is asphalt material or carbonaceous organic material; Described lithium carbonate comprises, one or more of the organic acid such as phosphate, nitrate, oxalates, sulfate, acetate, halide or inorganic acid lithium salts.
Described asphalt material is a kind of in high softening point bitumen, middle softening point asphalt, the low softening point asphalt.
Described carbonaceous organic material is a kind of in monosaccharide and disaccharide, the polysaccharide.
Advantage and good effect that the present invention has are:
Silica-base material of the present invention surface has not only coated the presoma of having selected material with carbon element, carbon, also in clad material, added lithium carbonate, the present invention has not only improved the coating of material to a great extent, and Effective Raise the tap density of material, energy density that can the Effective Raise lithium ion battery.
Description of drawings
Fig. 1 is the first all electrochemistry cyclic process curve charts of lithium ion battery negative material of the present invention and well known materials;
Fig. 2 is lithium ion battery negative material electrochemistry cyclic process curve chart of the present invention.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and cooperate accompanying drawing to be described in detail as follows:
A kind of lithium ion battery negative material comprises silica-base material, and the silica-base material surface is coated with the presoma of material with carbon element and carbon.
Innovative point of the present invention is: described silica-base material surface is coated with lithium carbonate; The mass ratio that the presoma of described silica-base material, material with carbon element, carbon and lithium carbonate mix is 5-10:5-10:15-30:1-2; Described silica-base material is polysilicon, monocrystalline silicon, or its mixture; Described material with carbon element is a kind of in Delanium, native graphite, carbon fiber, hard carbon, the agraphitic carbon; The presoma of described carbon is asphalt material or carbonaceous organic material; Described lithium carbonate comprises, one or more of the organic acid such as phosphate, nitrate, oxalates, sulfate, acetate, halide or inorganic acid lithium salts; Described asphalt material is a kind of in high softening point bitumen, middle softening point asphalt, the low softening point asphalt; Described carbonaceous organic material is a kind of in monosaccharide and disaccharide, the polysaccharide.
The manufacturing process of lithium ion battery negative material of the present invention:
⑴ with the 10g polysilicon, 10g graphite, and 30g coal tar pitch and 2.5g lithium acetate mix, and 100mL ethanolic solution ball milling 30 hours, heating detached ethanolic solution, obtains uniform presoma;
⑵ place high temperature furnace with the presoma of gained, and the lower 5 ℃/min of argon gas atmosphere is warmed up to 900 ℃, and high temperature sintering 5h makes silicon based anode material after the natural cooling down; After tested, the tap density of this material reaches more than the 1.0g/mL.Use this material to be prepared into lithium ion battery, the specific discharge capacity of this material reaches more than the 1000mAh/g, almost is 3 times of conventional carbon material.
Another manufacturing process of lithium ion battery negative material of the present invention:
⑴ with the 10g polysilicon, 10g graphite, and 40g coal tar pitch and 2.5g lithium acetate mix, and 100mL ethanolic solution ball milling 30 hours, heating detached ethanolic solution, obtains uniform presoma;
⑵ place high temperature furnace with the presoma of gained, and the lower 5 ℃/min of argon gas atmosphere is warmed up to 900 ℃, and high temperature sintering 5h makes silicon based anode material after the natural cooling down; After tested, the tap density of this material reaches 1.1g/mL.The sample capacity of this material and is not decayed in 10 week circulations about 950mAh/g; First all efficient 80.3%.
Fig. 1 is the first all electrochemistry cyclic process curve comparison diagrams of the present invention and well known materials, and wherein ascending curve is the trial curve that the present invention prepares material; Fig. 2 is the electrochemistry cyclic process curve chart of material of the present invention, and " " among the figure is that charging capacity, " ■ " are discharge capacity; Can find out by Fig. 1 and Fig. 2, negative material tap density of the present invention can reach more than the 1.0g/mL, and the specific discharge capacity of its material is almost 3 times of conventional carbon material greater than 950mAh/g.
Material preparation principle of the present invention: carbon class material in the presoma, can build regular carbon-coating structure in electrode material body interior and surface, improve the electric conductivity of material; Lithium salts can help to form the SEI film in surface and the oxide skin(coating) reaction of silicon grain as additive, reduces first embedding lithium reaction irreversible capacity; Material with carbon element and additive compound coating can be alleviated the reunion of silicon materials in electrochemical reaction effectively, improve the cycle life of silica-base material; The method of ball milling-sinter bonded, can either effectively reduce the cost of manufacture of material, can make again the granularity of material reach nano-scale, reduce the internal stress of material in electrochemical reaction, the trend of alleviation material efflorescence, the material granule surface is fully reacted with oxide skin(coating), form good film on the material granule surface, improve coating effect, jolt ramming and the compacted density of material.The present invention adopts the method for ball milling-sintering, adopt silicon, material with carbon element and on a small quantity as the lithium salts of additive as raw material, through ball milling and sintering processes, formed silicon-graphite-carbon-contain lithium ion battery silicon based anode material of lithium composite bed; The material of the present invention preparation have that first charge-discharge efficiency is high, under the prerequisite of good cycling stability, not only the cost of manufacture of material reduces, and the coating of material is effective, jolt ramming and compacted density are high, energy density that can the Effective Raise lithium ion battery, be fit to the needs that large-scale commercial applications is used, be high power, high-energy power consumption equipment, the basis of development is provided such as the development of electric motor car etc.
Although the above is described the preferred embodiments of the present invention by reference to the accompanying drawings; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make a lot of forms, these all belong within protection scope of the present invention.
Claims (5)
1. a lithium ion battery negative material comprises silica-base material, and the silica-base material surface is coated with the presoma of material with carbon element and carbon, it is characterized in that: described silica-base material surface is coated with lithium carbonate.
2. a kind of lithium ion battery negative material according to claim 1 is characterized in that: the mass ratio that the presoma of silica-base material, material with carbon element, carbon and lithium carbonate mix is 5-10:5-10:15-30:1-2.
3. a kind of lithium ion battery negative material according to claim 1 and 2, it is characterized in that: described silica-base material is polysilicon, monocrystalline silicon, or its mixture; Described material with carbon element is a kind of in Delanium, native graphite, carbon fiber, hard carbon, the agraphitic carbon; The presoma of described carbon is asphalt material or carbonaceous organic material; Described lithium carbonate comprises, one or more of the organic acid such as phosphate, nitrate, oxalates, sulfate, acetate, halide or inorganic acid lithium salts.
4. a kind of lithium ion battery negative material according to claim 3 is characterized in that: described asphalt material is a kind of in high softening point bitumen, middle softening point asphalt, the low softening point asphalt.
5. a kind of lithium ion battery negative material according to claim 2 is characterized in that: described carbonaceous organic material is a kind of in monosaccharide and disaccharide, the polysaccharide.
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| CN2012104641496A CN102931413A (en) | 2012-11-15 | 2012-11-15 | Lithium ion battery cathode material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015044618A1 (en) | 2013-09-30 | 2015-04-02 | Renault S.A.S | Electrode for an electric energy storage battery comprising a graphite/silicon/carbon fibre composite material |
| CN104538635A (en) * | 2014-12-11 | 2015-04-22 | 江西先材纳米纤维科技有限公司 | High-performance binder for silicon materials for lithium ion batteries and preparation method thereof |
| CN105633387A (en) * | 2014-11-04 | 2016-06-01 | 中国电子科技集团公司第十八研究所 | Preparation method of silicon-based anode material |
| CN105645379A (en) * | 2016-01-11 | 2016-06-08 | 神华集团有限责任公司 | Asphalt hard carbon material, and preparation method and application thereof |
| CN111029578A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Modified hard carbon negative electrode material and preparation method thereof |
| CN111416110A (en) * | 2020-04-02 | 2020-07-14 | 上海电气集团股份有限公司 | Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof |
| CN112652755A (en) * | 2019-10-09 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery |
| US11005097B2 (en) | 2012-08-21 | 2021-05-11 | Kratos LLC | Group IVA functionalized particles and methods of use thereof |
| CN113258069A (en) * | 2021-04-30 | 2021-08-13 | 合肥工业大学 | Negative electrode active material, method for preparing same, negative electrode, and secondary battery |
| WO2021192575A1 (en) * | 2020-03-26 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Negative electrode for secondary batteries, and secondary battery |
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- 2012-11-15 CN CN2012104641496A patent/CN102931413A/en active Pending
Patent Citations (3)
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| US20080070120A1 (en) * | 2006-09-14 | 2008-03-20 | Shin-Etsu Chemical Co., Ltd. | Non-aqueous electrolyte secondary battery and making method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11005097B2 (en) | 2012-08-21 | 2021-05-11 | Kratos LLC | Group IVA functionalized particles and methods of use thereof |
| WO2015044618A1 (en) | 2013-09-30 | 2015-04-02 | Renault S.A.S | Electrode for an electric energy storage battery comprising a graphite/silicon/carbon fibre composite material |
| CN105633387A (en) * | 2014-11-04 | 2016-06-01 | 中国电子科技集团公司第十八研究所 | Preparation method of silicon-based anode material |
| CN104538635A (en) * | 2014-12-11 | 2015-04-22 | 江西先材纳米纤维科技有限公司 | High-performance binder for silicon materials for lithium ion batteries and preparation method thereof |
| CN105645379A (en) * | 2016-01-11 | 2016-06-08 | 神华集团有限责任公司 | Asphalt hard carbon material, and preparation method and application thereof |
| CN112652755A (en) * | 2019-10-09 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery |
| CN112652755B (en) * | 2019-10-09 | 2022-07-12 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery |
| CN111029578A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Modified hard carbon negative electrode material and preparation method thereof |
| WO2021192575A1 (en) * | 2020-03-26 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Negative electrode for secondary batteries, and secondary battery |
| CN111416110A (en) * | 2020-04-02 | 2020-07-14 | 上海电气集团股份有限公司 | Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof |
| CN113258069A (en) * | 2021-04-30 | 2021-08-13 | 合肥工业大学 | Negative electrode active material, method for preparing same, negative electrode, and secondary battery |
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