CN110048114A - A kind of bivalve silicon carbon material and preparation method thereof - Google Patents

A kind of bivalve silicon carbon material and preparation method thereof Download PDF

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CN110048114A
CN110048114A CN201910361691.0A CN201910361691A CN110048114A CN 110048114 A CN110048114 A CN 110048114A CN 201910361691 A CN201910361691 A CN 201910361691A CN 110048114 A CN110048114 A CN 110048114A
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shell
bivalve
carbon material
kernel
preparation
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赵育松
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
University of Chinese Academy of Sciences
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Ningbo Institute of Material Technology and Engineering of CAS
University of Chinese Academy of Sciences
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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
    • 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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 present invention provides a kind of bivalve silicon carbon material, including kernel, the first shell being coated on outside kernel and the second shell being coated on outside the first shell；The kernel is SiOxMaterial and/or nano silicon particles；First shell is porous metal oxide；Second shell is carbon-coating.Compared with prior art, the present invention is by facilitating inner buffer layer SiO in kernel outer cladding porous metal oxidexThen material and/or the biggish volume expansion of nano silicon particles contribute to form relatively stable SEI film in porous metal oxide outer cladding carbon-coating, keep the stability of SEI film；Bivalve silicon carbon material is set both high rate performance with higher or to have there is preferable stability from there through above-mentioned duplex shell structure.

Description

A kind of bivalve silicon carbon material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of bivalve silicon carbon material and preparation method thereof.
Background technique
Currently, lithium ion battery has gradually incorporated each part of life as mature energy-storage units.In life The electric appliances such as mobile phone, notebook use lithium ion battery as its energy-storage units, and in recent years lithium ion battery also gradually by In terms of power energy storage, such as electric car.
For lithium ion battery, influencing most factors to its energy density should be positive electrode and negative electrode material. The graphite negative material of lithium ion battery that uses is commercialized at present, and there are lower theoretical capacities, further promote the sky of its capacity Between very little, far from meeting the needs of following high-capacity and long-life electronic equipment.Metal and alloy material are Recent studies More new and effective storage lithium titanate cathode material system, wherein silicon because have high theoretical specific capacity (4200mAh/g) due to by Concern, but it in embedding de- lithium, volume change is larger, and so that material structure is destroyed, electrode cycle performance sharply declines, from And the energy-storage property of battery is caused much to be not achieved using standard.
In order to overcome these deficiencies, researcher has carried out a large amount of trial, using Composite technology, " cushioning frame " is utilized to mend Repay material expansion.
Carbonaceous negative electrode material volume change in charge and discharge process is smaller, has preferable stable circulation performance, and carbon Matter negative electrode material itself is the mixed conductor of ion and electronics；In addition, silicon is close with carbon geochemistry property, the two can combine closely, Therefore carbon is commonly used for the preferred matrix compound with silicon.In silicon-carbon compound system, silicon particle provides storage lithium and holds as active material Amount；Carbon can buffer the volume change of silicium cathode in charge and discharge process and improve the electric conductivity of siliceous material, moreover it is possible to avoid silicon Particle is reunited in charge and discharge cycles.Therefore the advantages of Si-C composite material both combines, show height ratio capacity and Compared with long circulation life, it is expected to that graphite is replaced to become lithium ion battery negative material of new generation.
But current Si-C composite material for silicon materials volume expansion and high rate performance difference solution mainly still Nanosizing processing is carried out to silicon materials, carries out single layer carbon coating either Si/SiOx/ C one kind it is compound, cannot be more perfect change It is kind.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of high rate performance preferably and reducing silicon materials body The bivalve silicon carbon material and preparation method thereof of product expansion.
The present invention provides a kind of bivalve silicon carbon material, including kernel, the first shell for being coated on outside kernel be coated on The second shell outside first shell；The kernel is SiOxMaterial and/or nano silicon particles；First shell is porous metals Oxide；Second shell is carbon-coating.
Preferably, the mass ratio of the kernel and the first shell is 125:(0.5~1).
Preferably, first shell with a thickness of 1~2 μm；Second shell with a thickness of 2~3 μm.
Preferably, the porous metal oxide is porous aluminas.
The present invention also provides a kind of preparation methods of bivalve silicon carbon material, comprising:
S1) by SiOxMaterial and/or nano silicon particles, hydrolysis auxiliary agent are mixed with metal alkoxide in alcoholic solvent, are then added dropwise Water is hydrolyzed reaction, is precipitated；The hydrolysis auxiliary agent is itrogenous organic substance；
S2) described be deposited in protective atmosphere is calcined, obtains intermediate product；
S3) intermediate product is mixed in organic solvent with carbon source, after spray drying, is calcined in protective atmosphere, Obtain bivalve silicon carbon material.
Preferably, the step S1) in hydrolysis auxiliary agent and metal alkoxide mass ratio be 3:(0.5~1)；The metal alcohol Salt is aluminium-alcohol salt；The mass ratio of the water and metal alkoxide is 2:(0.5~1)；The step S3) in carbon source be selected from phenolic aldehyde tree One of rouge, sucrose and pitch are a variety of；The organic solvent in ethyl alcohol, N-Methyl pyrrolidone and hexamethylene one Kind is a variety of.
Preferably, the step S1) in be added dropwise water speed be 0.1~1g/min.
Preferably, the step S1) specifically:
By SiOxMaterial and/or nano silicon particles mixs 10~30min with hydrolysis auxiliary agent in alcoholic solvent, are then added golden Belong to alkoxide and mix 5~20min, then water is added dropwise, 3~5h of reaction is hydrolyzed, is precipitated.
Preferably, the step S2) in calcine temperature be 500 DEG C~700 DEG C；The time of calcining is 1~3h；Calcining Heating rate is 1~10 DEG C/min；
The step S3) in calcine temperature be 700 DEG C~1000 DEG C；The time of calcining is 10~30h；The heating of calcining Rate is 1~10 DEG C/min.
Preferably, the step S3) specifically:
The carbon source is mixed with organic solvent, obtains mixed liquor；The mass volume ratio of the carbon source and organic solvent is (0.1~0.5) g:1ml；
The intermediate product is mixed with mixed liquor, after spray drying, is calcined in protective atmosphere, bivalve silicon-carbon material is obtained Material.
The present invention provides a kind of bivalve silicon carbon material, including kernel, the first shell for being coated on outside kernel be coated on The second shell outside first shell；The kernel is SiOxMaterial and/or nano silicon particles；First shell is porous metals Oxide；Second shell is carbon-coating.Compared with prior art, the present invention in kernel outer cladding porous metals by aoxidizing Object facilitates inner buffer layer SiOxMaterial and/or the biggish volume expansion of nano silicon particles, then outside porous metal oxide Cladding carbon-coating contributes to form relatively stable SEI film, keeps the stability of SEI film；Make from there through above-mentioned duplex shell structure double Shell silicon carbon material both high rate performance with higher or had had preferable stability.
Detailed description of the invention
Fig. 1 is the cycle performance curve graph of bivalve silicon carbon material obtained in the embodiment of the present invention 1 and contrast groups.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
The present invention provides a kind of bivalve silicon carbon material, including kernel, the first shell for being coated on outside kernel be coated on The second shell outside first shell；The kernel is SiOxMaterial and/or nano silicon particles；First shell is porous metals Oxide；Second shell is carbon-coating.
According to the present invention, the bivalve silicon carbon material is with SiOxMaterial and/or nano silicon particles are kernel；The SiOxMaterial The partial size of material is preferably 1~3 μm.
The kernel is coated with the first shell；First shell is porous metal oxide, preferably porous oxidation Aluminium, more preferably porous gamma-Al2O3；The thickness of first shell is preferably 1~2 μm；The matter of the kernel and the first shell Amount is than being preferably 125:(0.5~1).
First shell is coated with the second shell；Second shell is carbon-coating；The thickness of the carbon-coating is preferably 2 ~3 μm.
The present invention is by facilitating inner buffer layer SiO in kernel outer cladding porous metal oxidexMaterial and/or silicon are received Then the biggish volume expansion of rice grain contributes to form relatively stable SEI film in porous metal oxide outer cladding carbon-coating, Keep the stability of SEI film；Had bivalve silicon carbon material both high rate performance with higher or from there through above-mentioned duplex shell structure There is preferable stability.
The present invention also provides a kind of preparation methods of above-mentioned bivalve silicon carbon material, comprising: S1) by SiOxMaterial and/or Nano silicon particles, hydrolysis auxiliary agent are mixed with metal alkoxide in alcoholic solvent, and water is then added dropwise, reaction is hydrolyzed, is precipitated；Institute Stating hydrolysis auxiliary agent is itrogenous organic substance；S2) described be deposited in protective atmosphere is calcined, obtains intermediate product；S3) in will be described Between product mixed in organic solvent with carbon source, after spray drying, calcined in protective atmosphere, obtain bivalve silicon carbon material.
The present invention is not particularly limited the source of all raw materials, is commercially available.
According to the present invention, preferably first by SiOxMaterial and/or nano silicon particles mix in alcoholic solvent with hydrolysis auxiliary agent；Institute State SiOxThe partial size of material is preferably 1~3 μm；The hydrolysis auxiliary agent is itrogenous organic substance, preferably polyvinylpyrrolidone；Institute Stating alcoholic solvent is preferably ethyl alcohol；The volume and SiO of the alcoholic solventxThe ratio of material and/or nano silicon particles is preferably (200~500) ml:(100~200) g, more preferably (300~400) ml:(100~160) g is further preferably 350ml:(120 ~130) g, most preferably 350ml:125g；The mixed time is preferably 10~30min, more preferably 15~25min, then Preferably 20min.
After mixing, metal alkoxide mixing is added；The metal alkoxide is preferably aluminium-alcohol salt, more preferably aluminium isopropoxide；Institute State SiOxThe mass ratio of material and/or nano silicon particles and metal alkoxide is preferably 125:(0.5~1), more preferably 125: (0.6~0.8) is further preferably 125:(0.6~0.7), most preferably 125:(0.66~0.68)；The hydrolysis auxiliary agent and metal The mass ratio of alkoxide is preferably 3:(0.5~1), more preferably 3:(0.6~0.8), it is further preferably 3:(0.6~0.7) and, most preferably For 3:(0.66~0.68)；The mixed time is preferably 5~20min, more preferably 8~15min, further preferably for 10~ 12min。
Then water is added dropwise, reaction is hydrolyzed；The mass ratio of the water and metal alkoxide is preferably 2:(0.5~1), it is more excellent It is selected as 2:(0.6~0.8), be further preferably 2:(0.6~0.7), most preferably 2:(0.66~0.68)；The speed that water is added dropwise Preferably 0.1~1g/min, more preferably 0.2~0.8g/min are further preferably 0.4~0.6g/min；The hydrolysis Time is preferably 3~5h, more preferably 3.5~4.5h, is further preferably 4h.
After the completion of hydrolysis, preferably sedimentation removal clear liquid is precipitated after dry；The temperature of the drying is preferably 50 DEG C~70 DEG C, more preferably 60 DEG C.
Described be deposited in protective atmosphere is calcined；The protective atmosphere is preferably argon gas；The flow of the protective atmosphere Preferably 10~30ml/min, more preferably 15~25ml/min are further preferably 20ml/min；The temperature of the calcining is preferably 500 DEG C~700 DEG C, more preferably 550 DEG C~650 DEG C, be further preferably 600 DEG C；The time of the calcining is preferably 1~3h, more Preferably 1.5~2.5h is further preferably 2h；The heating rate of the calcining is preferably 1~10 DEG C/min, more preferably 2~8 DEG C/min, and it is further preferably 4~6 DEG C/min, most preferably 5 DEG C/min.
It after calcining, is preferably sieved, obtains intermediate product；The mesh number of the sieving is preferably 400 mesh.
The intermediate product is mixed in organic solvent with carbon source；In the present invention, it is preferred to first by the carbon source with have Solvent mixing, obtains mixed liquor；Then the intermediate product is mixed with mixed liquor；The carbon source be preferably phenolic resin, One of sucrose and pitch are a variety of；The organic solvent is preferably volatile organic solvent, more preferably ethyl alcohol, N- first One of base pyrrolidones and hexamethylene are a variety of；The mass volume ratio of the carbon source and organic solvent be preferably (0.1~ 0.5) g:1ml, more preferably (0.2~0.4) g:1ml are further preferably (0.3~0.35) g:1ml；The carbon source and organic solvent The mixed time is preferably 2~6h, more preferably 3~5h, is further preferably 4h；The intermediate product is mixed with mixed liquor；Institute The ratio for stating intermediate product and mixed liquor be preferably after making cladding carbon-coating with a thickness of 2~3 μm；The intermediate product and mixed liquor The mixed time is preferably 2~6h, more preferably 3~5h, is further preferably 4h.
After mixing, it is spray-dried；The spray drying carries out preferably in spray-dried instrument；When the spray drying It is preferred that dry with the flow velocity of 10~20ml/min, more preferably 13~17ml/min is further preferably 15ml/min.
It after spray drying, is calcined in protective atmosphere, obtains bivalve silicon carbon material.The protective atmosphere is preferably argon gas； The temperature of the calcining is preferably 700 DEG C~1000 DEG C, and more preferably 800 DEG C~1000 DEG C, be further preferably 900 DEG C；It is described to forge The time of burning is preferably 10~30h, more preferably 15~30h, is further preferably 20~28h, most preferably for 24 hours；The calcining Heating rate is preferably 1~10 DEG C/min, more preferably 2~8 DEG C/min, is further preferably 2~6 DEG C/min, is further preferably 2~4 DEG C/min, most preferably 3 DEG C/min.
In order to further illustrate the present invention, with reference to embodiments to a kind of bivalve silicon carbon material provided by the invention and its Preparation method is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1.1 by 1~3 μm of 125g SiOxPVP (polyvinylpyrrolidone) dispersing and dissolving with 3g is at ethyl alcohol (400mL) In, stir 20min；0.6735g AIP (aluminium isopropoxide) is added and dissolves 10min；2gH is added dropwise2O has added (purpose in 5min It is to promote to hydrolyze)；After clock reaction h, sedimentation removal clear liquid；60 DEG C be dried to bulk after take out, precipitated.
The precipitating is warming up to 600 DEG C of (throughput 20ml/min) calcining 2h under an ar atmosphere with 5 DEG C/min by 1.2. After calcining, sieving (mesh number is 400 mesh) retains screenings after sieving, obtains intermediate product.
1.3 are dissolved in phenolic resin in ethyl alcohol (ratio are as follows: 100g:300ml), and 4h is stirred in timing, obtain mixed liquor；It will Intermediate material in 1.2 dissolves in mixed liquor, and 4h is stirred in timing；It is with flow velocity in spray-dried instrument by the liquid stirred evenly 15ml/min is dry, collects dried object；It is calcined for 24 hours in the case where 3 DEG C/min of batch-type furnace temperature programming rises to 900 DEG C of Ar atmosphere, Sieving is taken out, bivalve silicon carbon material is obtained.
Contrast groups are that the partial size of unprocessed mistake is 1~3 μm of SiOx, it is denoted as contrast groups 1.
The partial size of bivalve carbon silicon materials and the unprocessed mistake of contrast groups that embodiment 1 is obtained is 1~3 μm of SiOxIt makes respectively For at detaining battery and being detected to its performance, obtains its cycle performance curve graph and be shown in Table as shown in Figure 1, obtaining charge-discharge performance 1；Wherein detain battery size CR2430；Electrolyte: LiPF6:EC:DEC:PP=1:1.78:3.57:1.4；Cathode proportion: Bivalve carbon silicon materials obtained in the embodiment 1 of PAA3.0%, SP 1.0%, CMC 3.0% and surplus or unprocessed mistake The SiO that partial size is 1~3 μmx；To electrode: pour lithium slice.
1 different materials of table buckle electrical testing charge-discharge performance
From Fig. 1 and table 1: when SOC is 100%, the pole piece for the bivalve silicon carbon material that embodiment 1 obtains is expanded to 35.2%；Contrast groups pole piece is expanded to 48.8%；It is 150mA/cm in current density2Under, final product gram volume is 1835mAh；Contrast groups gram volume is 1407mAh；The first charge discharge efficiency for the bivalve silicon carbon material that embodiment 1 obtains is 84%, comparison The first charge discharge efficiency of group is 78%；150mA/cm2After lower circulation 50cls, final product capacity is maintained at 1432mAh, and coulomb Efficiency is maintained at 99.5% or more, and comparison pool-size remains less than 900mAh；After 100cls circulation, dismantling pole piece measurement is implemented The bivalve silicon carbon material pole piece that example 1 obtains is expanded to 45.3%, and contrast groups pole piece is expanded to 72.3%.
2~embodiment of embodiment 5
The preparation method is the same as that of Example 1, and the calcination temperature after only changing cladding phenolic resin obtains bivalve silicon carbon material.
Phenolic resin difference calcination temperature charge-discharge performance after table 2 coats
Heating rate is influence of the calcination temperature different under 3 DEG C/min to silicon carbon material charge-discharge performance as shown in Table 2: Phosphorus content is 15.3wt% after 600 DEG C of cracking；Carbon content is 10.5~10.7wt% after 700~800 DEG C of cracking；900 DEG C split Carbon content drops to 9.6wt% after solution；When being warming up to 1000 DEG C, carbon content is only 6.3wt%；Furthermore cracking temperature is to carbonization temperature Degree also has an impact, and 600 DEG C of cracking degree are minimum, and carbon content and hydrogen content are higher, it is generally the case that the low carbon material of carbonizing degree Circulation degree is more unstable.

Claims (10)

1. a kind of bivalve silicon carbon material, which is characterized in that including kernel, the first shell for being coated on outside kernel and be coated on first The second shell outside shell；The kernel is SiOxMaterial and/or nano silicon particles；First shell is porous metals oxidation Object；Second shell is carbon-coating.
2. bivalve silicon carbon material according to claim 1, which is characterized in that the mass ratio of the kernel and the first shell is 125:(0.5~1).
3. bivalve silicon carbon material according to claim 1, which is characterized in that first shell with a thickness of 1~2 μm； Second shell with a thickness of 2~3 μm.
4. bivalve silicon carbon material according to claim 1, which is characterized in that the porous metal oxide is porous oxidation Aluminium.
5. a kind of preparation method of bivalve silicon carbon material characterized by comprising
S1) by SiOxMaterial and/or nano silicon particles, hydrolysis auxiliary agent are mixed with metal alkoxide in alcoholic solvent, and water is then added dropwise, into Row hydrolysis, is precipitated；The hydrolysis auxiliary agent is itrogenous organic substance；
S2) described be deposited in protective atmosphere is calcined, obtains intermediate product；
S3) intermediate product is mixed in organic solvent with carbon source, after spray drying, calcines, obtains in protective atmosphere Bivalve silicon carbon material.
6. preparation method according to claim 5, which is characterized in that the step S1) in hydrolysis auxiliary agent and metal alkoxide Mass ratio be 3:(0.5~1)；The metal alkoxide is aluminium-alcohol salt；The mass ratio of the water and metal alkoxide be 2:(0.5~ 1)；The step S3) in carbon source be selected from one of phenolic resin, sucrose and pitch or a variety of；The organic solvent is selected from One of ethyl alcohol, N-Methyl pyrrolidone and hexamethylene are a variety of.
7. preparation method according to claim 5, which is characterized in that the step S1) in be added dropwise water speed be 0.1~ 1g/min。
8. preparation method according to claim 5, which is characterized in that the step S1) specifically:
By SiOxMaterial and/or nano silicon particles mixs 10~30min with hydrolysis auxiliary agent in alcoholic solvent, then addition metal alcohol Salt mixes 5~20min, then water is added dropwise, and 3~5h of reaction is hydrolyzed, is precipitated.
9. preparation method according to claim 5, which is characterized in that the step S2) in calcine temperature be 500 DEG C~ 700℃；The time of calcining is 1~3h；The heating rate of calcining is 1~10 DEG C/min；
The step S3) in calcine temperature be 700 DEG C~1000 DEG C；The time of calcining is 10~30h；The heating rate of calcining For 1~10 DEG C/min.
10. preparation method according to claim 5, which is characterized in that the step S3) specifically:
The carbon source is mixed with organic solvent, obtains mixed liquor；The mass volume ratio of the carbon source and organic solvent is (0.1 ~0.5) g:1ml；
The intermediate product is mixed with mixed liquor, after spray drying, is calcined in protective atmosphere, obtains bivalve silicon carbon material.
CN201910361691.0A 2019-04-30 2019-04-30 A kind of bivalve silicon carbon material and preparation method thereof Pending CN110048114A (en)

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CN102054983A (en) * 2009-10-28 2011-05-11 信越化学工业株式会社 Negative electrode material for non-aqueous electrolyte secondary batteries, manufacturing method therefor, and lithium-ion secondary batteries
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CN107623104A (en) * 2017-09-25 2018-01-23 常州市宇科不绣钢有限公司 A kind of structure silicon-based negative material of multi-buffer and preparation method thereof
CN109616623A (en) * 2018-10-31 2019-04-12 深圳市德方纳米科技股份有限公司 A kind of silicon-based anode material and preparation method thereof

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WO2020125621A1 (en) * 2018-12-17 2020-06-25 Ningde Amperex Technology Limited Anode material, electrochemical device and electronic device using the same
CN111149241A (en) * 2019-12-30 2020-05-12 上海杉杉科技有限公司 Silicon-based lithium storage material and preparation method thereof
WO2021134195A1 (en) * 2019-12-30 2021-07-08 上海杉杉科技有限公司 Silicon-based lithium-storage material and preparation method therefor
CN111149241B (en) * 2019-12-30 2023-11-28 上海杉杉科技有限公司 Silicon-based lithium storage material and preparation method thereof
WO2022000589A1 (en) * 2020-06-29 2022-01-06 瑞声声学科技(深圳)有限公司 Method for preparing silicon-based composite negative electrode material
CN113363437A (en) * 2021-05-18 2021-09-07 恒大新能源技术(深圳)有限公司 Silicon-based negative electrode material and preparation method thereof, negative plate and secondary battery
CN113991095A (en) * 2021-12-28 2022-01-28 安普瑞斯（南京）有限公司 Negative active material, preparation method thereof, electrode and battery

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Application publication date: 20190723