CN105870422A - C@SiOx material, preparation method thereof and application of C@SiOx material taken as negative electrode material of lithium ion battery - Google Patents
C@SiOx material, preparation method thereof and application of C@SiOx material taken as negative electrode material of lithium ion battery Download PDFInfo
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- CN105870422A CN105870422A CN201610383086.XA CN201610383086A CN105870422A CN 105870422 A CN105870422 A CN 105870422A CN 201610383086 A CN201610383086 A CN 201610383086A CN 105870422 A CN105870422 A CN 105870422A
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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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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 discloses a C@SiOx material, a preparation method thereof and application of the C@SiOx material taken as the negative electrode material of a lithium ion battery, and belongs to the preparation of renewable energy materials and the application of the materials in the lithium ion battery. The production process of the C@SiOx material comprises the steps of immersing silicon-containing biomass by tap water to remove soil in the silicon-containing biomass; soaking biomass raw material by an acid to remove metal impurities introduced in the agricultural production process, and carbonizing in a tube furnace; then activating the carbonized biomass by using an activating agent to obtain carbonized biomass; reducing by using active metal powder after activation, thus obtaining the C@SiOx negative electrode material of the lithium ion battery.
Description
Technical field
The present invention relates to the recovery energy of renewable silicon containing biomass, particularly relate to a kind of C@SiOxMaterial and system thereof
Preparation Method and the application as lithium ion battery negative material, belong to the preparation of renewable energy source material and at lithium-ion electric
Application aspect in pond.
Background technology
Silicon containing biomass is mainly derived from the residue of the production process of cereal crops.As a example by rice husk, China according to statistics
Current rice annual production has been over 100,018,000 tons, accounts for 1/3rd of whole world gross annual output amount, occupies the world
The first.Having substantial amounts of rice husk during Rice producing to produce, Oryza glutinosa per ton can produce the rice husk of about 200kg.This
A little rice husks are due to little (the about 120Kg/m of its natural deposited dry density3), bring great inconvenience to transport.And the opposing party
Face, rice husk is utilized by a most Rice Milling Enterprises not technique the most effective, then a lot of rice
Shell is taken as agricultural wastes to have suffered to abandon.Along with the development of China's paddy processing technology, Rice Milling Enterprises gradually increases
Many, the scale of enterprise is also gradually increased so that day processing rice amount gradually increases, and these factories have to process every day
The rice husk of at least 20～80 tons.The rice husk that accumulates over a long period stockpiles too much, in case of the environment of surrounding can be caused certain journey by wind and rain
The pollution of degree, how processing these rice husks has become the problem that processing enterprise must solve.Along with rice husk utilizes technology
Development and the progress of energy-conserving and environment-protective consciousness, rice husk starts to be used by more domestic grain processing enterprises.Common do
Method is, using rice husk as a kind of biomass fuel, is burnt or is pyrolyzed as generating or produces preboiled rice offer energy.
The pollution problem of environment is resolved by rice husk outwardly, and some resources in rice husk have also been obtained part and utilize,
But still suffer from environmental pollution, also need further agricultural wastes to be comprehensively utilized.
Silicon containing biomass is mainly made up of silicon dioxide and organic principle (cellulose, lignin and hemicellulose), also
There is least a portion of metal and an ash.Silicon dioxide is evenly distributed in Organic substance, if by its carbonization, can obtain
To uniform carbon bag silicon dioxide structure, if by the most permissible for the silicon containing biomass active metal powder reduction after carbonization
Obtain uniform carbon bag silicon dioxide and the triplet composite of silicon or uniform carbon bag silicon composite, both materials
Material can serve as the negative material of lithium ion battery, overcomes the bulk effect of pure silicon negative material and the low of pure material with carbon element
Capacity problem.
People disclose the preparation method of multiple carbon/silicon lithium ion battery cathode material the most in succession at present,
CN103022446A discloses a kind of lithium ion battery silicon oxide/carbon negative material and preparation method thereof (Yue Min etc.
[P])；CN103682359A discloses a kind of oxide S iOxWith the preparation method of material with carbon element, wherein, 1≤x≤2
(Chen Pu, Li Mingqi [P])；CN103531754A discloses a kind of graphene/silicon dioxide/copper/silicon/soft carbon
The preparation method (Shu Jie, Liu Wang just wait [P]) of lamination composite negative pole material；CN102867947A discloses a kind of base
Preparation method (Yang Yang, the few husband of model waits [P]) in the carbon/silicon composite cathode material of oligomeric silsesquioxane.These are prepared
Method is all to utilize chemical reagent as carbon source and silicon source, utilizes complex building-up process to prepare carbon/silicon lithium ion electricity
Pond negative material.The present invention is to use silicon containing biomass directly to prepare carbon/silicon lithium ion battery cathode material.
Patent ZL101804988B discloses a kind of new method (king utilizing rice hull ash to prepare silicon dioxide and activated carbon
Sub-sincere feeling, Liu Yan etc. [P])；CN201110436706.9 discloses a kind of rice husk thermal decomposition ash synchronization and prepares waterglass and activity
The straightforward procedure (prince's sincere feeling, Liu Yan etc. [P]) of charcoal.Above-mentioned patent directly prepares lithium ion without reference to utilizing biomass
Cell negative electrode material.
Summary of the invention
It is an object of the invention to for the reproducible silicon containing biomass being widely present, to transportation, natural environment and
The healthy negative effect brought of people, it is contemplated that silicon containing biomass mainly containing silicon dioxide and Organic substance (cellulose,
Hemicellulose and lignin) this two class may utilize material, it is provided that and one makes full use of silicon containing biomass to prepare C@SiOx
The method of lithium ion battery negative material, wherein, 0≤x < 2.The method of the present invention directly utilizes biomass and prepares carbon bag
Covering silicon oxide compound, it is not necessary to complicated bag carbon process, technique is simple, with low cost, can realize technical process environmental protection without
Pollute.
The present invention is achieved through the following technical solutions:
The present invention provides one to utilize silicon containing biomass to prepare C@SiOxThe side of (0≤x < 2) lithium ion battery negative material
Method, described technical process is with biomass as raw material, environment friendly and pollution-free；Chemical reagent used in technical process is cheap；
Technical process is simple.Wherein, 0≤x < 2；Technical process is with the biomass of dioxide-containing silica >=10% as raw material, logical
Cross washing, be dried, pulverize after, carbonization 1～4h at 450～600 DEG C, then at 500～800 DEG C activate 1～
4h, finally with active metal 650～800 DEG C of reduction 1～4h, prepares C@SiOxMaterial；Described dioxy
SiClx content is the mass percent relative to over dry raw material.
One of the present invention utilizes silicon containing biomass to prepare C@SiOxThe method of lithium ion battery negative material, tool
Body step is:
A) soak the earth removed in silicon containing biomass raw material with tap water, acid soak removes the metal impurities in raw material
After, at 100 DEG C, it is vacuum dried 12h, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material.
B) pure powdered biomass is put into argon as protection gas tube furnace in, carbonization at 450～600 DEG C
1～4h；
C) mix with the carbonization biomass in mass ratio 1～4:1 obtained in step b with activator, add distilled water immersion
8～24h, after being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 500～800 DEG C,
Activation 1～4h；Carbonization biomass after activating with distilled water wash, remove activator；At 100 DEG C of vacuum drying ovens
In be dried 12h；
D) the porous silicon carbide biomass obtained in step c are mixed all in the ratio of 1:0.1～1 with active metal powder
Even, load in homemade metal reaction still, the reactor of charging is put into argon as protection gas tube furnace in,
650～800 DEG C of reduction 1～4h；Then the metal-oxide generated in reduction reaction and the metal of excess are removed by acid solution
Powder, after distilled water wash, is dried 12h in the vacuum drying oven of 50 DEG C and obtains C@SiOxLithium ion battery is born
Pole material.
Preferably, of the present invention silicon containing biomass is utilized to prepare C@SiOxThe method of lithium ion battery negative material,
Described silicon containing biomass is one or more mixture of wheat husk, rice husk, oat shell, Semen avenae nudae shell；
Preferably, of the present invention silicon containing biomass is utilized to prepare C@SiOxThe method of lithium ion battery negative material,
Described activator is K2CO3、KOH、H3PO4、ZnCl.Described metal dust be magnesium powder, aluminium powder, iron powder or
Zinc powder.The metal-oxide generated in described removing reduction reaction and the acid of excess metal powder are hydrochloric acid, nitric acid or sulfur
Acid, concentration is 0.5～3mol/L；
Preferably, in step d, described metal reaction still material is 430 rustless steels, for cylinder, kettle and kettle cover
By screw thread compact siro spinning technology.
The present invention provides the C@SiO that a kind of above-mentioned preparation method obtainsxMaterial.
The present invention provides a kind of above-mentioned C@SiOxMaterial is as the application of lithium ion battery negative material.
Invention beneficial effect
1. the raw materials used China's the earth that spreads all over of the present invention, cheap and easily-available.
2. the chemical reagent used by the present invention is cheap, and experimentation no waste is discharged, Environmental Safety.
3. the lithium ion battery negative material prepared by the present invention, specific capacity is 3 times of conventional graphite material, bears than silicon
The good cycling stability of pole material, high-performance is excellent, beneficially expanding production.
Accompanying drawing explanation
Accompanying drawing 3 width of the present invention,
Fig. 1 is the C@SiO of preparationxThe technological process of lithium ion battery negative material；
Fig. 2 is the C SiO prepared by embodiment 3xLithium ion battery negative material SEM schemes；
Fig. 3 is the C SiO prepared by embodiment 3xLithium ion battery negative material XRD figure.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material,
If no special instructions, the most commercially obtain；
Reactor used, for homemade 430 stainless steel cauldrons, journey is cylindrical, and kettle and kettle cover are tight by screw thread
Connect, still wall thickness 0.3 centimetre, diameter 2.5 centimetres, long 3.5 centimetres.
Dioxide-containing silica >=10% in biomass material used.
Embodiment 1
1. the earth removed in rice husk is soaked with tap water, after acid soak removes the metal impurities in rice husk, at 100 DEG C
Lower vacuum drying 12h, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material.
2. pure powdered rice hulls is put into argon as protection gas tube furnace in, carbonization 3h at 450 DEG C；
3. K is used2CO3Mix with the carbonization rice husk obtained in step b 2:1 in mass ratio, add distilled water immersion 8h,
After being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 600 DEG C, activate 1h；With
Carbonization rice husk after distilled water wash activation, removes activator；12h it is dried in 100 DEG C of vacuum drying ovens；
4. by step 3. in the porous silicon carbide rice husk that obtains mix homogeneously in the ratio of 1:0.1 with iron powder, load homemade gold
Belong in reactor, the reactor of charging is put into argon as in the tube furnace of protection gas, reduce 3h at 650 DEG C；So
The ferrum oxide generated in reduction reaction and the iron powder of excess is removed afterwards with 2mol/L hydrochloric acid solution, after distilled water wash,
In the vacuum drying oven of 50 DEG C, it is dried 12h obtains C@SiOxLithium ion battery negative material.
Embodiment 2
1. the earth removed in wheat husk is soaked with tap water, after acid soak removes the metal impurities in wheat husk, at 100 DEG C
Lower vacuum drying 12h, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material.
2. pure wheat husk powder is put into argon as protection gas tube furnace in, carbonization 2h at 550 DEG C；
3. K is used2CO3Mix with the carbonization wheat husk 3:1 in mass ratio obtained in step b, add distilled water immersion 12h,
After being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 500 DEG C, activate 1.5h；With
Carbonization wheat husk after distilled water wash activation, removes activator；12h it is dried in 100 DEG C of vacuum drying ovens；
4. by step 3. in the porous silicon carbide wheat husk that obtains mix homogeneously in the ratio of 1:0.3 with aluminium powder, load homemade gold
Belong in reactor, the reactor of charging is put into argon as in the tube furnace of protection gas, reduce 3h at 700 DEG C；So
The aluminium oxide generated in reduction reaction and the aluminium powder of excess is removed afterwards with 1mol/L hydrochloric acid solution, after distilled water wash,
In the vacuum drying oven of 50 DEG C, it is dried 12h obtains C@SiOxLithium ion battery negative material.
Embodiment 3
1. the earth removed in oat shell is soaked with tap water, after acid soak removes the metal impurities in oat shell,
Being vacuum dried 12h at 100 DEG C, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material.
2. pure oat shell powder is put into argon as protection gas tube furnace in, carbonization 2h at 500 DEG C；
3. mix with the carbonization oat shell 4:1 in mass ratio obtained in step b with ZnCl, add distilled water immersion 14h,
After being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 700 DEG C, activate 2h；With
Carbonization oat shell after distilled water wash activation, removes activator；12h it is dried in 100 DEG C of vacuum drying ovens；
4. by step 3. in the porous silicon carbide oat shell that obtains mix homogeneously in the ratio of 1:0.5 with magnesium powder, load homemade
In metal reaction still, the reactor of charging is put into argon as protection gas tube furnace in, at 750 DEG C of reductase 12 h；
Then remove the magnesium oxide generated in reduction reaction and the magnesium powder of excess with 1mol/L salpeter solution, use distilled water wash
After, the vacuum drying oven of 50 DEG C is dried 12h and obtains C@SiOxLithium ion battery negative material.
Embodiment 4
1. the earth removed in Semen avenae nudae shell is soaked with tap water, after acid soak removes the metal impurities in Semen avenae nudae shell,
Being vacuum dried 12h at 100 DEG C, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material.
2. pure Semen avenae nudae shell powder is put into argon as protection gas tube furnace in, carbonization 1h at 550 DEG C；
3. mix with the carbonization Semen avenae nudae shell 3:1 in mass ratio obtained in step b with ZnCl, add distilled water immersion 16h,
After being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 700 DEG C, activate 1h；With
Carbonization Semen avenae nudae shell after distilled water wash activation, removes activator；12h it is dried in 100 DEG C of vacuum drying ovens；
4. by step 3. in the porous silicon carbide Semen avenae nudae shell that obtains mix homogeneously in the ratio of 1:0.7 with magnesium powder, load homemade
In metal reaction still, the reactor of charging is put into argon as protection gas tube furnace in, 800 DEG C reduce 1h；
Then remove the magnesium oxide generated in reduction reaction and the magnesium powder of excess with 1mol/L sulfuric acid solution, use distilled water wash
After, the vacuum drying oven of 50 DEG C is dried 12h and obtains C@SiOxLithium ion battery negative material.
Embodiment 5
1. the earth removed in wheat husk is soaked with tap water, after acid soak removes the metal impurities in wheat husk, at 100 DEG C
Lower vacuum drying 12h, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material.
2. pure wheat husk powder is put into argon as protection gas tube furnace in, carbonization 3h at 500 DEG C；
3. mix with the carbonization wheat husk 4:1 in mass ratio obtained in step b with ZnCl, add distilled water immersion 24h,
After being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 750 DEG C, activate 1h；With
Carbonization wheat husk after distilled water wash activation, removes activator；12h it is dried in 100 DEG C of vacuum drying ovens；
4. by step 3. in the porous silicon carbide wheat husk that obtains mix homogeneously in the ratio of 1:0.7 with aluminium powder, load homemade gold
Belong in reactor, the reactor of charging is put into argon as in the tube furnace of protection gas, reduce 3h at 650 DEG C；So
The aluminium oxide generated in reduction reaction and the aluminium powder of excess is removed afterwards with 2mol/L sulfuric acid solution, after distilled water wash,
In the vacuum drying oven of 50 DEG C, it is dried 12h obtains C@SiOxLithium ion battery negative material.
Gained C@SiO in table 1 embodimentxMiddle C, Si, O tri-element mass percent and the value of x.
Gained C@SiO in table 2 embodimentxThe electrochemical properties of lithium ion battery negative material, lists with 0.1A/g
Charge-discharge velocity when carrying out discharge and recharge, the 50th time, 100 times and the specific capacity of 150 times.
Claims (8)
1. one kind utilizes silicon containing biomass to prepare C SiOxThe method of material, wherein, 0≤x < 2；Technical process be with
The biomass of dioxide-containing silica >=10% are raw material, after washing, be dried, pulverizing, and carbon at 450～600 DEG C
Change 1～4h, then at 500～800 DEG C activate 1～4h, finally with active metal 650～800 DEG C reduction 1～
4h, prepares C@SiOxMaterial；Described dioxide-containing silica is the mass percent relative to over dry raw material.
Preparation method the most according to claim 1, it is characterised in that: described silicon containing biomass raw material be wheat husk,
Rice husk, oat shell, one or more mixture of Semen avenae nudae shell.
Preparation method the most according to claim 1, it is characterised in that: described preparation C@SiOxThe step of material
Suddenly it is:
A) silicon containing biomass raw material washs through tap water, soaks after removing metal impurities with acid solution, at 100 DEG C
Vacuum drying 12h, after pulverizing with plant pulverizer, the powder taking 60 eye mesh screens is raw material；
B) pure powdered biomass is put into argon as protection gas tube furnace in, carbonization at 450～600 DEG C
1～4h；
C) mix with the carbonization biomass in mass ratio 1～4:1 obtained in step b with activator, add distilled water immersion
8～24h, after being dried 8h at 100 DEG C；Put in the argon tube furnace as protection gas, at 500～800 DEG C,
Activation 1～4h；Carbonization biomass after activating with distilled water wash, remove activator；At 100 DEG C of vacuum drying ovens
In be dried 12h；
D) the porous silicon carbide biomass obtained in step c are mixed all in the ratio of 1:0.1～1 with active metal powder
Even, load in metal reaction still, the reactor of charging put into argon as in the tube furnace of protection gas, 650～
800 DEG C of reduction 1～4h；Then the metal-oxide generated in reduction reaction and the metal dust of excess are removed by acid solution,
After distilled water wash, the vacuum drying oven of 50 DEG C is dried 12h and obtains C@SiOxMaterial.
Preparation method the most according to claim 3, it is characterised in that:
In step c, described activator is selected from K2CO3、KOH、H3PO4、ZnCl；
In step d, described metal dust is selected from magnesium powder, aluminium powder, iron powder or zinc powder.
Preparation method the most according to claim 3, it is characterised in that: described for removing generation in reduction reaction
Metal-oxide and the acid of excess metal powder be hydrochloric acid, nitric acid or sulphuric acid, concentration is 0.5～3mol/L.
Preparation method the most according to claim 3, it is characterised in that: in step d, described metal reaction still material
Matter is 430 rustless steels, for cylinder, kettle and kettle cover by screw thread compact siro spinning technology.
7. the C@SiO that preparation method as described in claim 1～6 any one claim obtainsxMaterial.
8. C@SiO as claimed in claim 7xMaterial is as the application of lithium ion battery negative material.
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| CN106299283A (en) * | 2016-09-07 | 2017-01-04 | 扬州大学 | The ball-milling preparation method of hole, rice husk Quito silicon nano material |
| CN106299327A (en) * | 2016-10-10 | 2017-01-04 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method of lithium ion battery anode material |
| CN106450188A (en) * | 2016-10-10 | 2017-02-22 | 东莞市凯金新能源科技股份有限公司 | Preparation method of positive electrode material of lithium-ion battery |
| CN107140963A (en) * | 2017-04-20 | 2017-09-08 | 常州创索新材料科技有限公司 | A kind of preparation method of compound electromagnetic wave transparent material |
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| CN109713259A (en) * | 2018-12-10 | 2019-05-03 | 华南农业大学 | A kind of silicon-carbon composite cathode material of lithium ion battery and its preparation method and application |
| CN109935811A (en) * | 2019-03-11 | 2019-06-25 | 内蒙古科技大学 | A method of lithium ion battery negative material is prepared using silicon containing biomass |
| CN110112376A (en) * | 2019-03-25 | 2019-08-09 | 华南农业大学 | A kind of preparation method and application of porous oxidation Asia silicon/carbon compound cathode materials |
| CN110429264A (en) * | 2019-08-13 | 2019-11-08 | 吉林大学 | A method of preparing rice husk base negative electrode material |
| CN110690439A (en) * | 2019-10-25 | 2020-01-14 | 河南大森林生物科技有限公司 | P, N co-doped C/SiO prepared from silicon-containing biomassxGreen method for composite negative electrode material of lithium ion battery |
| CN110867567A (en) * | 2019-10-25 | 2020-03-06 | 湖北万润新能源科技发展有限公司 | High-safety SiO synthesized by biomass siliconxPreparation method and application of @ C material |
| CN111082000A (en) * | 2019-11-29 | 2020-04-28 | 湖北万润新能源科技发展有限公司 | Preparation method for optimizing SiOx @ C performance by using pore-forming agent |
| CN111422875A (en) * | 2020-02-25 | 2020-07-17 | 上海恒仑新能源科技有限公司 | Preparation method of biological silicon monoxide and product thereof |
| CN111916735A (en) * | 2019-05-09 | 2020-11-10 | 贝特瑞新材料集团股份有限公司 | Amorphous carbon material, preparation method thereof and lithium ion battery |
| CN112599751A (en) * | 2020-12-30 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silicon dioxide/C composite material for lithium ion battery cathode, product and application thereof |
| CN114188524A (en) * | 2021-12-09 | 2022-03-15 | 泉州师范学院 | Method for preparing microelement-doped silicon-carbon negative electrode material from sludge |
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