CN108565408A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN108565408A CN108565408A CN201810021428.2A CN201810021428A CN108565408A CN 108565408 A CN108565408 A CN 108565408A CN 201810021428 A CN201810021428 A CN 201810021428A CN 108565408 A CN108565408 A CN 108565408A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery negative material and preparation method thereof.The negative material of the present invention uses the structure of three layers of three-dimensional globular of carbon silicon-carbon, and most one layer of the inside is graphitic carbon, for providing volume expansion space of silicon during insertion/deintercalate lithium ions；Intermediate one layer is amorphous silicon, as the lithium ion that cathode is used to receive to come from anode migration, realizes energy storage；Outermost one layer deposits carbon for pyrolytic carbon or PECVD, for providing stable skeleton structure, to ensure the stability of silicon cathode entirety during expansion and diminution, and the generation for phenomena such as preventing dusting and fall off from microcosmic.The negative material structure design of the present invention, both the silicon advantage big as cathode specific capacity had been ensure that, space is provided for the volume expansion of silicon with the soft yielding feature of graphite again, also further ensures the stability of negative material entirety as skeleton with the carbon with some strength.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery negative material and its preparation side
Method.
Background technology
From the nineties in last century can safe utilization graphite cathode invention since, it is lower removal lithium embedded current potential, suitable
Reversible capacity, higher first charge discharge efficiency and cyclical stability and have many advantages, such as it is resourceful, cheap pushed lithium from
Large-scale application of the sub- battery in fields such as personal electronic equipments.
In the 21st century, is growing with high-energy-density 3C Product and electric vehicle, graphite-like carbon material negative pole theory ratio
The low disadvantage of capacity (372mAh/g) gradually highlights, and seriously limits the development of the extensive energy storage of lithium ion battery.At the same time,
Silicon is because having higher theoretical specific capacity (4200mAh/g), rich reserves and cheap to become the cathode material by extensive concern
One of material.However, the shortcomings that silicium cathode material, is more apparent, during lithium ion deintercalation its there are huge volume expansions to imitate
It answers, lead to the dusting of silica-base material and falls off so that specific capacity and coulombic efficiency are constantly decayed, and cycle life is poor.Therefore, right
Silica-base material modification reduces the Volumetric expansion during its insertion/deintercalation and becomes solving silicon based anode material and answer
Key technology.
Invention content
For above-mentioned there are problem or deficiency, to solve to manage existing for graphite-like carbon negative pole material in existing lithium ion battery
By the technical issues of specific capacity is low and the expansion of silicium cathode material volume, the present invention provides a kind of lithium ion battery negative material and
Preparation method, the negative material use the structure of three layers of three-dimensional globular of carbon-silico-carbo.
The microstructure of the lithium ion battery negative material is three layers of clad structure of carbon-silico-carbo, and most one layer of the inside is graphite
Carbon, it is more soft yielding, for providing volume expansion space of silicon during insertion/deintercalate lithium ions；Intermediate one layer is
Amorphous silicon realizes energy storage as the lithium ion that cathode is used to receive to come from anode migration；Outermost one layer is with relatively stable
The pyrolytic carbon or PECVD of structure deposit carbon, for providing stable skeleton structure, to ensure silicon during expansion and diminution
The stability of cathode entirety, the generation for phenomena such as preventing dusting and fall off from microcosmic.
Preparation method 1 is as follows：
Step 1, by the graphite as carbon source with amorphous silicon as silicon source according to 1:1-1:After 5 ratio prepares, system
At nano level hybrid fine particles.
Hybrid fine particles addition dispersant is then dissolved in organic solvent and is uniformly mixed.Then it is dried, then will dry
Mixture sintering afterwards obtains the graphite particulate of amorphous silicon cladding.
Step 1 gained graphite particulate is mixed by stirring evenly in cold primer-oil by step 2, then under vacuum conditions
Being heated to 70-100 DEG C makes it be completely dried, the presoma that carbon-silico-carbo to obtain solid-state phase coats.
Step 2 gained presoma is added heat preservation by step 3 at 200-300 DEG C, is then heated to heat under protection of argon gas
Solution.It is several microns of particles to tens micron grain sizes to get to target product amorphous carbon-amorphous state that product after pyrolysis, which crushes,
The three-dimensional spherical structure negative material of three layers of silicon-graphitic carbon.
Preparation method 2 is as follows：
Nano level uniform microparticle will be made as the graphite of internal layer carbon source in step 1.
Step 2 with PECVD methods using silane is silicon source in step 1 gained microparticle outer layer deposited amorphous state silicon layer.
Step 3 with PECVD methods using methane and hydrogen is carbon source again in the amorphous silicon layer of step 2 gained microparticle
Several microns of amorphous carbon-three layers of amorphous silicon-graphitic carbon three-dimensionals to tens micron grain sizes are finally made in external sediment outermost layer carbon
Spherical structure negative material.
The special negative material structure design of the present invention not only ensure that the silicon advantage big as cathode specific capacity, but also use
The soft yielding feature of graphite is that the volume expansion of silicon provides space, also with the carbon with some strength as skeleton into
One step ensure that the stability of negative material entirety.
Description of the drawings
The three-dimensional spherical structure negative material schematic diagram of three layers of Fig. 1 carbon-silico-carbos of the present invention.
Specific implementation mode
Present invention is further described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1：
Step 1, graphite and amorphous silicon are according to 1:3 ratio, which prepares, is put into ball milling 24 hours in ball mill, and 80- is made
The hybrid fine particles of 100 nanometer particle sizes.
Hybrid fine particles and dispersant are dissolved in ethyl alcohol and water with obtaining mixed solution, and stirred evenly by step 2.
Step 2 gained mixed solution is spray-dried by step 3.
Gained mixture in step 3 is sintered by step 4, obtains the graphite particulate of amorphous silicon cladding.
Step 4 gained graphite particulate is uniformly blended by mechanical agitation in cold primer-oil and under vacuum conditions by step 5
80 DEG C of dryings 3 hours are heated to, carbon-silico-carbo to obtain solid-state phase coats presoma.
Presoma in step 5 is added heat preservation 3 hours by step 6 at 250 DEG C, is then heated to 1050 under protection of argon gas
DEG C pyrolysis.
Step 7 sieves crushed rear 300 mesh of crossing of the product after step 6 pyrolysis, so that it may obtain target product amorphous carbon-
The three-dimensional spherical structure negative material of three layers of amorphous silicon-graphitic carbon.
Embodiment 2：
Step 1 will be put into ball milling 24 hours in ball mill as the graphite of internal layer carbon source, and it is equal that 80-100 nanometer particle sizes are made
Even microparticle.
Step 2 with PECVD methods using silane is silicon source in these uniform microparticle outer layer deposited amorphous state silicon layers.
Step 3, the microparticle for having outer silicon to deposition obtained by step 2 using methane and hydrogen as carbon source with PECVD methods
Deposit outermost layer carbon, you can obtain the three-dimensional spherical structure negative material of amorphous carbon-three layers of amorphous silicon-graphitic carbon.
The amorphous carbon finally prepared-three layers of amorphous silicon-graphitic carbon three-dimensional spherical shape its structure of negative material such as Fig. 1 institutes
Show.
Claims (3)
1. a kind of lithium ion battery negative material, it is characterised in that：
Microstructure is three layers of clad structure of carbon-silico-carbo, and most one layer of the inside is graphitic carbon, for providing silicon in insertion/removal lithium embedded
Volume expansion space during ion；Intermediate one layer is amorphous silicon, is used to receive to come from anode migration as cathode
Lithium ion realizes energy storage；Outermost one layer deposits carbon for pyrolytic carbon or PECVD, for providing stable skeleton structure, to ensure silicon
The stability of cathode entirety during expansion and diminution, the generation for phenomena such as preventing dusting and fall off from microcosmic.
2. the preparation method of lithium ion battery negative material as described in claim 1, includes the following steps：
Step 1, by the graphite as carbon source with amorphous silicon as silicon source according to 1:1-1:After 5 ratio prepares, it is made and receives
The hybrid fine particles of meter level；
Hybrid fine particles addition dispersant is then dissolved in organic solvent and is uniformly mixed, is then dried, then will be after drying
Mixture sintering obtains the graphite particulate of amorphous silicon cladding；
Step 1 gained graphite particulate is mixed by stirring evenly in cold primer-oil by step 2, is then heated under vacuum conditions
It is set to be completely dried to 70-100 DEG C, the presoma that carbon-silico-carbo to obtain solid-state phase coats；
Step 2 gained presoma is added heat preservation by step 3 at 200-300 DEG C, is then heated to being pyrolyzed under protection of argon gas, heat
It is several microns of particles to tens micron grain sizes to get to target product amorphous carbon-amorphous silicon-stone that product after solution, which crushes,
The three-dimensional spherical structure negative material of three layers of black carbon.
3. the preparation method of lithium ion battery negative material as described in claim 1, includes the following steps：
Nano level uniform microparticle will be made as the graphite of internal layer carbon source in step 1；
Step 2 with PECVD methods using silane is silicon source in step 1 gained microparticle outer layer deposited amorphous state silicon layer；
Step 3 is sunk outside the amorphous silicon layer of step 2 gained microparticle using methane and hydrogen as carbon source again with PECVD methods
It is three-dimensional spherical that several microns of amorphous carbon-three layers of amorphous silicon-graphitic carbons to tens micron grain sizes are finally made in product outermost layer carbon
Structure negative material.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110880592A (en) * | 2019-12-03 | 2020-03-13 | 哈尔滨工业大学 | Carbon-carbon nanotube-silicon nanoparticle and preparation method and application thereof |
| CN111333063A (en) * | 2020-02-25 | 2020-06-26 | 广东东岛新能源股份有限公司 | Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof |
| CN111816856A (en) * | 2020-07-21 | 2020-10-23 | 深圳先进技术研究院 | Composite material, preparation method thereof and negative electrode |
| CN111834613A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
| CN111925232A (en) * | 2020-07-24 | 2020-11-13 | 江西昌大高新能源材料技术有限公司 | Graphite surface silicon/carbon double-layer coated negative electrode material and preparation method thereof |
| CN112234171A (en) * | 2020-09-08 | 2021-01-15 | 中南大学 | Silicon-natural graphite composite material, application thereof and method for preparing silicon-natural graphite composite material by catalyzing with trace harmless impurities |
| CN112635733A (en) * | 2020-12-21 | 2021-04-09 | 江苏集芯半导体硅材料研究院有限公司 | Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery |
| CN112661132A (en) * | 2020-12-23 | 2021-04-16 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based composite negative electrode material and preparation method thereof |
| CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111834613A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
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| CN111333063A (en) * | 2020-02-25 | 2020-06-26 | 广东东岛新能源股份有限公司 | Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof |
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| CN111925232A (en) * | 2020-07-24 | 2020-11-13 | 江西昌大高新能源材料技术有限公司 | Graphite surface silicon/carbon double-layer coated negative electrode material and preparation method thereof |
| CN112234171A (en) * | 2020-09-08 | 2021-01-15 | 中南大学 | Silicon-natural graphite composite material, application thereof and method for preparing silicon-natural graphite composite material by catalyzing with trace harmless impurities |
| CN112234171B (en) * | 2020-09-08 | 2022-04-08 | 中南大学 | Silicon-natural graphite composite material, application thereof and method for preparing silicon-natural graphite composite material by catalyzing with trace harmless impurities |
| CN112635733A (en) * | 2020-12-21 | 2021-04-09 | 江苏集芯半导体硅材料研究院有限公司 | Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery |
| CN112635733B (en) * | 2020-12-21 | 2021-12-31 | 江苏集芯半导体硅材料研究院有限公司 | Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery |
| CN112661132A (en) * | 2020-12-23 | 2021-04-16 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based composite negative electrode material and preparation method thereof |
| CN112661132B (en) * | 2020-12-23 | 2023-05-09 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based composite anode material and preparation method thereof |
| CN114335533A (en) * | 2021-12-16 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative electrode material and battery comprising same |
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