CN106058256A - Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery - Google Patents
Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery Download PDFInfo
- Publication number
- CN106058256A CN106058256A CN201610567050.7A CN201610567050A CN106058256A CN 106058256 A CN106058256 A CN 106058256A CN 201610567050 A CN201610567050 A CN 201610567050A CN 106058256 A CN106058256 A CN 106058256A
- Authority
- CN
- China
- Prior art keywords
- preparation
- porous silicon
- acid
- iron
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the technical field of preparation of lithium ion batteries, and particularly relates to a preparation method of a carbon nanotube composite porous silicon anode material for a lithium ion battery. The preparation method mainly comprises the following steps: preparing porous silicon by thermal reduction; coating the porous silicon with carbon by chemical vapor deposition and compounding carbon nanotubes; removing an iron catalyst by acid treatment. The preparation technology is low in energy consumption and cost, reversible capacity of the silicon anode material is increased effectively, the rate capability is improved, and the cycle life is prolonged. Primary particle sizes of the prepared porous silicon are 50-500 nm, a uniform carbon layer with the thickness range of 2-50 nm is deposited on the surface of the porous silicon, and the carbon nanotubes are distributed inside and outside particles, so that overall electronic conductivity of the porous silicon is improved.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery negative material carbon nanotube
The preparation method of compound porous silicon.
Background technology
The negative material of commercial li-ion battery is mostly Delanium or native graphite now, and its theoretical specific capacity is
372 mAh·g-1, to lithium current potential at about 0.5 V, and silicon is 4200 as the specific capacity of lithium ion battery negative material
mAh·g-1, to lithium current potential at about 0.2 V, contrast the former, with the obvious advantage.Because the superelevation specific capacity of silicon materials and electronegative potential,
Become the most classic lithium ion battery negative material.But, exactly because silicon materials are available for lithium ion deintercalation
Measure huge so that it is in charge and discharge process, create the volumetric expansion under huge bulk effect theoretical capacity left 400%
Right.
The most industrial method preparing silicon materials has following several: the Silicon stone that reduces in (1) electric arc furnace (is mainly composed of two
Silicon oxide)；(2) electronics industry uses SiCl3H or SiCl4H2Reduction reaction forms high purity single crystal silicon；(3) magnesiothermic reduction dioxy
SiClx.The silicon grain that first method prepares is relatively big, becomes apparent from, easily at battery as its volumetric expansion of electrode material
Discharge and recharge causes electrode material efflorescence, makes battery inactivate；Second method cost intensive, is only applicable to prepare electron level monocrystalline
Silicon；The raw material that first scheme uses is cheap commercialization raw material, can prepare once by controlling the particle diameter of raw material
Particle diameter is at the porous silicon of 100 below nm, and the hole in porous silicon can provide the cushion space that material expands: substantially solve silicon
The bottleneck that material brings as commercialization Cost Problems and the intrinsic attribute of lithium ion battery, is that one preferably prepares lithium ion
The battery method of silicium cathode material.
The present invention first passes through the business-like magnesium powder of use and silicon dioxide mixing carries out magnesium thermit and is prepared for porous silicon,
Then by supported ferric catalyst, then the method carrying out chemical gaseous phase deposition carries out the on-the-spot life of bag carbon and CNT to material
Long.This programme adds the electrical contact site outside porous silicon hole and in hole in synthesis, is beneficial to its multidigit point and carries out embedding lithium,
Alleviate volumetric expansion stress, the electrode structure of stable silicon negative pole.The porous silicon primary particle size that prepared CNT is combined can
As little as 50 nm, even pore distribution, carbon-coating is evenly coated, and CNT is evenly distributed, Stability Analysis of Structures, has good electrification
Learn performance.
Summary of the invention
It is an object of the invention to provide one and prepare the compound porous silicon of lithium ion battery negative material carbon nanotube
Method, to improve silicon materials structural stability during removal lithium embedded, improve material electronic conductivity, improve its electrification
Learn performance, increase its commercial feasibility.
Technical scheme is as follows:
(1) commercialization silicon dioxide and magnesium powder are mixed by certain molar ratio, after being fully ground, protect at inert atmosphere
Protect down and carry out magnesium thermit and prepare porous silicon, be designated as pSS；
(2) porous silicon will be prepared to mix with soluble iron compound in the liquid phase, then liquid phase will be evaporated, obtain load iron oxygen
Compound or the porous silicon of hydroxide；
(3) porous silicon preparing supported ferriferous oxide or hydroxide is calcined under reducing atmosphere, iron compound is reduced
For ferrum, obtain the porous silicon of supported ferric catalyst；
(4) porous silicon of supported ferric catalyst is calcined in the inert atmosphere containing carbon-source gas, deposit carbon at particle surface
Layer, and situ growth CNT under the effect of iron catalyst, then by product pickling, obtain CNT after drying and be combined
Porous silicon, be designated as pSS/SNT.
In step of the present invention (1), described silicon dioxide and magnesium powder particle size range are in 10 nm-50 μm.
In step of the present invention (1), the molar ratio range of described silicon dioxide and magnesium powder is at 0.1-10.
In step of the present invention (1), described magnesium thermit temperature is 550-950 DEG C, and the response time is 2-10 h.
In step of the present invention (1), (4), described inert atmosphere is selected from nitrogen, argon, hydrogen-argon-mixed, hydrogen, artificial sky
One in gas.
In step of the present invention (2), described iron compound is selected from ferric nitrate, Ferrox., iron sulfate, ferrous sulfate, chlorination
One or more in ferrum, iron phosphate.
In step of the present invention (2), described liquid phase is in water, ethanol, methanol, isopropanol, acetone, normal hexane, benzene, toluene
One or more.
In step of the present invention (3), described reducibility gas is selected from hydrogen, hydrogen-argon-mixed, carbon monoxide gas, hydrogen nitrogen mixing
One in gas, methane nitrogen mixture, acetylene argon gaseous mixture.
In step of the present invention (3), described calcining heat is 500 DEG C-900 DEG C, and calcination time is 2-8 h.
In step of the present invention (4), described carbon-source gas is in toluene, benzene, methane, acetylene, ethanol, propanol, isopropanol
One or more.
In step of the present invention (4), described calcining heat is 650 DEG C-950 DEG C, and calcination time is 5-60 min.
In step of the present invention (4), described acid is in hydrochloric acid, sulphuric acid, phosphoric acid, chloroazotic acid, Fluohydric acid., acetic acid, oxalic acid, formic acid
One or more.
The present invention is that the porous silicon preparing magnesiothermy carries out the modification of further surface so that it is more applicable as lithium-ion electric
The preparation method of pond negative material.The porous silicon primary particle size prepared by magnesiothermy simple, low energy consumption can as little as 50
Nm, and the change in volume that abundant, the uniform pore passage structure having can be alleviated in silicon materials in removal lithium embedded.Whole synthesis side
Case low raw-material cost, equipment is simple, can serve as commercialization and prepares the promising approach of silicium cathode material.
Additionally, the present invention disposably completes the cladding of the carbon to material surface also by chemical vapour deposition technique and scene is raw
Long CNT, enhances the electronic conductivity of material.The CNT that especially situ growth obtains, it is evenly distributed in
Inside and outside porous silicon duct, by increasing capacitance it is possible to increase the electrical contact site within duct, it is ensured that porous silicon can be carried out in many sites simultaneously
Embedding lithium, alleviates the volumetric stress that the embedding lithium of integral material expands.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of each product in embodiment 2.
Fig. 2 is end product cycle life test data under 0.5 A/g electric current density in embodiment 2.
Fig. 3 is end product high rate performance test data under different electric current densities in embodiment 2.
Fig. 4 is the SEM image of end product in embodiment 2.
Fig. 5 is the TEM image of end product in embodiment 2.
Detailed description of the invention
Combine accompanying drawing hereafter by specific embodiment and further describe the present invention, be not intended that limitation of the present invention.
Embodiment 1
(1) weigh magnesium powder 15 g of silica 10 g, the 250-300 mesh that particle diameter is 200 nm, be placed in agate mortar grinding
Uniformly, then being placed in corundum crucible by mixed-powder, be placed in tube furnace, logical nitrogen is as protective gas, respectively at 700 DEG C
High temperature sintering 6 h, obtains the powder of porous silicon and by-product thereof；
(2) the powder hydrochloric acid obtained in (1) is removed unreacted magnesium powder and by-product magnesium oxide, and drying obtains pSS；
(3) evaporating water after the pSS obtained in (2) being mixed homogeneously in water with ferrous sulfate.Again mix powder is put
In tube furnace, logical hydrogen is as reducing gas, and high temperature sintering 6 h at 700 DEG C, obtains supported ferric catalyst many respectively
Hole silicon；
(4) porous silicon of the supported ferric catalyst obtained in (3) is placed in tube furnace, ventilating methane and mixed gas 1-of nitrogen
High temperature sintering 20 min at 3h, then 750 DEG C, obtains carbon cladding, and the porous silicon of situ growth CNT；
(5) product obtained in (4) impregnated in 10 h in aqueous sulfuric acid, it is compound many that sucking filtration drying obtain CNT
Hole silicon pSS/SNT.
Embodiment 2
(1) weigh magnesium powder 4.5 g of silicon dioxide 5 g, the 100-200 mesh that particle diameter is 7 nm, be placed in agate mortar grinding all
Even, then mixed-powder is placed in corundum crucible, it is placed in tube furnace, logical hydrogen-argon-mixed as protective gas, at 550 DEG C,
Lower high temperature sintering 10 h, obtains the powder of porous silicon and by-product thereof；
(2) the powder hydrochloric acid obtained in (1) is removed unreacted magnesium powder and by-product magnesium oxide, then remove not with Fluohydric acid.
Reaction silicon dioxide, and dry obtain pSS；
(3) pSS obtained in (2) is evaporated at water with ferric nitrate after mixing homogeneously in alcohol mixed solution.Again by mixture
Powder is placed in tube furnace, logical hydrogen-argon-mixed as reducing gas, and high temperature sintering 8 h at 500 DEG C obtains load iron and urges
The porous silicon of agent；
(4) porous silicon of the supported ferric catalyst obtained in (3) is placed in tube furnace, logical toluene and hydrogen-argon-mixed mixing
Gas 3 h, high temperature sintering 60 min at 650 DEG C, obtain carbon cladding, and the porous silicon of situ growth CNT；
(5) product obtained in (4) impregnated in 20 h in aqueous hydrochloric acid solution, it is compound many that sucking filtration drying obtain CNT
Hole silicon pSS/SNT.
Embodiment 3
(1) the silica 1 g that particle diameter is 100 nm is weighed, magnesium powder 1.2 g of 100-200 mesh, it is placed in agate mortar grinding
Uniformly, then being placed in corundum crucible by mixed-powder, be placed in tube furnace, logical argon is as protective gas, high at 950 DEG C
Temperature sintering 2 h, obtain the powder of porous silicon and by-product thereof；
(2) the powder nitric acid obtained in (1) is removed unreacted magnesium powder and by-product magnesium oxide, then remove not with Fluohydric acid.
Reaction silicon dioxide, and dry obtain pSS；
(3) it is evaporated after the pSS obtained in (2) being mixed homogeneously in the mixed solution of water and isopropanol with iron chloride.Again will be mixed
Compound powder is placed in tube furnace, and logical carbon monoxide is as reducing gas, and at 900 DEG C, high temperature sintering 2 h, obtains load iron
The porous silicon of catalyst；
(4) porous silicon of the supported ferric catalyst obtained in (3) is placed in tube furnace, logical acetylene and hydrogen-argon-mixed mixing
Gas 3 h, then high temperature sintering 5 min at 950 DEG C, obtain carbon cladding, and the porous silicon of situ growth CNT；
(5) product obtained in (4) impregnated in 5 h in phosphate aqueous solution, it is compound many that sucking filtration drying obtain CNT
Hole silicon pSS/SNT.
Claims (10)
1. the preparation method of a lithium ion battery CNT compound porous silicium cathode material, it is characterised in that concrete steps
For:
(1) silicon dioxide and magnesium powder are mixed, after being fully ground, under inert atmosphere protection, carry out magnesium thermit, preparation
Obtain porous silicon, be designated as pSS；
(2) porous silicon will be prepared to mix with soluble iron compound in the liquid phase, then liquid phase will be evaporated, obtain load iron oxygen
Compound or the porous silicon of hydroxide；
(3) porous silicon preparing supported ferriferous oxide or hydroxide is calcined under reducing atmosphere, iron compound is reduced
For ferrum, obtain the porous silicon of supported ferric catalyst, be designated as pSS/ iron catalyst；
(4) porous silicon of supported ferric catalyst is calcined in the inert atmosphere containing carbon-source gas, deposit carbon at particle surface
Layer, and situ growth CNT under the effect of iron catalyst, then by product pickling, obtain CNT after drying and be combined
Porous silicon, be designated as pSS/CNT.
Preparation method the most according to claim 1, it is characterised in that the silicon dioxide used in step (1) and magnesium powder
Particle size range in 10 nm-50 μm.
Preparation method the most according to claim 1 and 2, it is characterised in that the silicon dioxide used in step (1) and magnesium
The mol ratio of powder is 0.1-10.
Preparation method the most according to claim 3, it is characterised in that the inert atmosphere used in step (1), (4) is
One in nitrogen, argon, hydrogen-argon-mixed, hydrogen, artificial air.
5. according to the preparation method described in claim 1,2 or 4, it is characterised in that the iron compound used in step (2) is
One or more in ferric nitrate, Ferrox., iron sulfate, ferrous sulfate, iron chloride, iron phosphate；The liquid phase used be water,
One or more in ethanol, methanol, isopropanol, acetone, normal hexane, benzene, toluene.
Preparation method the most according to claim 5, it is characterised in that the reducibility gas used in step (3) is hydrogen
One in argon-mixed, carbon monoxide gas, hydrogen nitrogen mixed gas, methane nitrogen mixture, acetylene argon gaseous mixture.
7. according to the preparation method described in claim 1,2,4 or 6, it is characterised in that in step (3), described calcining heat is
500 DEG C-900 DEG C, calcination time is 2-8 h.
Preparation method the most according to claim 7, it is characterised in that the carbon-source gas used in step (4) be toluene,
One or more in benzene, methane, acetylene, ethanol, propanol, isopropanol.
9. according to the preparation method described in claim 1,2,4,6 or 8, it is characterised in that in step (4), described calcining heat
Being 650 DEG C-950 DEG C, calcination time is 5-60 min.
Preparation method the most according to claim 9, it is characterised in that the acid used in step (4) be hydrochloric acid, sulphuric acid,
One or more in phosphoric acid, chloroazotic acid, Fluohydric acid., acetic acid, oxalic acid, formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610567050.7A CN106058256A (en) | 2016-07-19 | 2016-07-19 | Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610567050.7A CN106058256A (en) | 2016-07-19 | 2016-07-19 | Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106058256A true CN106058256A (en) | 2016-10-26 |
Family
ID=57187827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610567050.7A Pending CN106058256A (en) | 2016-07-19 | 2016-07-19 | Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106058256A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248570A (en) * | 2017-05-26 | 2017-10-13 | 华中科技大学 | A kind of core shell structure Si/C materials, preparation method and application |
| CN108365186A (en) * | 2018-01-11 | 2018-08-03 | 湖南立方新能源科技有限责任公司 | A kind of silicon substrate composite negative pole material and preparation method thereof |
| CN110518213A (en) * | 2019-08-30 | 2019-11-29 | 深圳市德方纳米科技股份有限公司 | A kind of porous silicon-carbon nano tube compound material and its preparation method and application |
| CN110817845A (en) * | 2019-11-19 | 2020-02-21 | 厦门大学 | Amorphous hollow carbon nanotube and preparation method thereof |
| 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 |
| CN111525121A (en) * | 2020-05-10 | 2020-08-11 | 兰溪致德新能源材料有限公司 | Silicon anode material with villus structure and preparation method thereof |
| CN111653735A (en) * | 2020-02-24 | 2020-09-11 | 深圳市翔丰华科技股份有限公司 | Low-temperature carbon-coated porous silicon composite negative electrode material and preparation method thereof |
| CN114122357A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof |
| CN114314564A (en) * | 2021-12-22 | 2022-04-12 | 长沙晟天新材料有限公司 | Carbon nanotube conductive network coated SiO @ C composite material and preparation method and application thereof |
| CN114447304A (en) * | 2022-01-28 | 2022-05-06 | 蜂巢能源科技股份有限公司 | Hard carbon composite negative electrode material and preparation method and application thereof |
| KR20220080564A (en) * | 2020-12-07 | 2022-06-14 | 재단법인 한국탄소산업진흥원 | Method for manufacturing silicon and carbon nanotube composite composition for lithium battery negative electrode |
| WO2022156152A1 (en) * | 2021-01-20 | 2022-07-28 | 惠州市豪鹏科技有限公司 | Silicon composite material, preparation method therefor, negative plate and lithium ion battery |
| WO2023130851A1 (en) * | 2022-01-04 | 2023-07-13 | 宁德时代新能源科技股份有限公司 | Silicon negative electrode material, and secondary battery, battery module, battery pack and electric device comprising same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185128A (en) * | 2011-04-02 | 2011-09-14 | 上海交通大学 | Silicon carbon composite material and preparation method thereof |
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
| CN105529447A (en) * | 2016-01-21 | 2016-04-27 | 昆明理工大学 | Preparation method and application of carbon nanotube-carbon-porous silicon composite material |
-
2016
- 2016-07-19 CN CN201610567050.7A patent/CN106058256A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185128A (en) * | 2011-04-02 | 2011-09-14 | 上海交通大学 | Silicon carbon composite material and preparation method thereof |
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
| CN105529447A (en) * | 2016-01-21 | 2016-04-27 | 昆明理工大学 | Preparation method and application of carbon nanotube-carbon-porous silicon composite material |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107248570B (en) * | 2017-05-26 | 2020-02-21 | 华中科技大学 | Core-shell structure Si/C material, preparation method and application |
| CN107248570A (en) * | 2017-05-26 | 2017-10-13 | 华中科技大学 | A kind of core shell structure Si/C materials, preparation method and application |
| CN108365186A (en) * | 2018-01-11 | 2018-08-03 | 湖南立方新能源科技有限责任公司 | A kind of silicon substrate composite negative pole material and preparation method thereof |
| CN110518213A (en) * | 2019-08-30 | 2019-11-29 | 深圳市德方纳米科技股份有限公司 | A kind of porous silicon-carbon nano tube compound material and its preparation method and application |
| CN110817845A (en) * | 2019-11-19 | 2020-02-21 | 厦门大学 | Amorphous hollow carbon nanotube and preparation method thereof |
| 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 |
| CN111653735A (en) * | 2020-02-24 | 2020-09-11 | 深圳市翔丰华科技股份有限公司 | Low-temperature carbon-coated porous silicon composite negative electrode material and preparation method thereof |
| CN111525121B (en) * | 2020-05-10 | 2022-02-15 | 兰溪致德新能源材料有限公司 | Silicon anode material with villus structure and preparation method thereof |
| CN111525121A (en) * | 2020-05-10 | 2020-08-11 | 兰溪致德新能源材料有限公司 | Silicon anode material with villus structure and preparation method thereof |
| KR20220080564A (en) * | 2020-12-07 | 2022-06-14 | 재단법인 한국탄소산업진흥원 | Method for manufacturing silicon and carbon nanotube composite composition for lithium battery negative electrode |
| KR102413542B1 (en) | 2020-12-07 | 2022-06-24 | 재단법인 한국탄소산업진흥원 | Method for manufacturing silicon and carbon nanotube composite composition for lithium battery negative electrode |
| WO2022156152A1 (en) * | 2021-01-20 | 2022-07-28 | 惠州市豪鹏科技有限公司 | Silicon composite material, preparation method therefor, negative plate and lithium ion battery |
| CN114122357A (en) * | 2021-11-10 | 2022-03-01 | 云南中晟新材料有限责任公司 | Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof |
| CN114314564A (en) * | 2021-12-22 | 2022-04-12 | 长沙晟天新材料有限公司 | Carbon nanotube conductive network coated SiO @ C composite material and preparation method and application thereof |
| CN114314564B (en) * | 2021-12-22 | 2023-11-28 | 湖南京舟股份有限公司 | Carbon nanotube conductive network coated SiO@C composite material and preparation method and application thereof |
| WO2023130851A1 (en) * | 2022-01-04 | 2023-07-13 | 宁德时代新能源科技股份有限公司 | Silicon negative electrode material, and secondary battery, battery module, battery pack and electric device comprising same |
| CN114447304A (en) * | 2022-01-28 | 2022-05-06 | 蜂巢能源科技股份有限公司 | Hard carbon composite negative electrode material and preparation method and application thereof |
| CN114447304B (en) * | 2022-01-28 | 2024-04-12 | 蜂巢能源科技股份有限公司 | Hard carbon composite anode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106058256A (en) | Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery | |
| Park et al. | Flexible dimensional control of high‐capacity Li‐ion‐battery anodes: From 0D hollow to 3D porous germanium nanoparticle assemblies | |
| JP5826405B2 (en) | Nanosilicon carbon composite material and method for preparing the same | |
| Lu et al. | Macroporous Co3O4 platelets with excellent rate capability as anodes for lithium ion batteries | |
| Song et al. | Porous nano-Si/carbon derived from zeolitic imidazolate frameworks@ nano-Si as anode materials for lithium-ion batteries | |
| Su et al. | Scalable synthesis of micrometer-sized porous silicon/carbon composites for high-stability lithium-ion battery anodes | |
| CN108269989B (en) | Carbon-coated micron silicon, and preparation method and application thereof | |
| CN105514403B (en) | A kind of three-dimensional nucleocapsid MoO2-MoS2Lithium ion battery negative material and preparation method thereof | |
| CN110112378B (en) | Silica composite negative electrode material of lithium ion battery and preparation method thereof | |
| Zhao et al. | Compact Si/C anodes fabricated by simultaneously regulating the size and oxidation degree of Si for Li-ion batteries | |
| Wang et al. | Microwave-assisted hydrothermal synthesis of porous SnO2 nanotubes and their lithium ion storage properties | |
| Wang et al. | Influence of carbon sources on LiFePO4/C composites synthesized by the high-temperature high-energy ball milling method | |
| CN107565136B (en) | A kind of porous Si-C composite material preparation method and products thereof based on rectorite | |
| CN107565115A (en) | Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material | |
| Xie et al. | A facile fabrication of micro/nano-sized silicon/carbon composite with a honeycomb structure as high-stability anodes for lithium-ion batteries | |
| Yin et al. | Nano MgFe 2 O 4 synthesized by sol–gel auto-combustion method as anode materials for lithium ion batteries | |
| CN105705460A (en) | Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom | |
| Ren et al. | Novel silicon/carbon nano-branches synthesized by reacting silicon with methyl chloride: A high performing anode material in lithium ion battery | |
| Yao et al. | Template-assisted synthesis of hierarchically porous Co3O4 with enhanced oxygen evolution activity | |
| CN102790211B (en) | Preparation method of high-performance copper ferrite ultrafine powder for lithium ion battery cathode materials | |
| CN110336003A (en) | A kind of porous silicon-base composite material and preparation method and application | |
| Fu et al. | Glucose assisted synthesis of hollow spindle LiMnPO4/C nanocomposites for high performance Li-ion batteries | |
| Li et al. | Simple synthesis of rice husk hollow carbon-coated flower ZnO for the anode in a high performance lithium-ion battery | |
| Wang et al. | Fabrication of one-dimensional CdFe 2 O 4 yolk/shell flat nanotubes as a high-performance anode for lithium-ion batteries | |
| Shao et al. | SiC/C composite mesoporous nanotubes as anode material for high-performance lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161026 |