CN104103819A - Silicon-carbon complex and preparation method thereof - Google Patents
Silicon-carbon complex and preparation method thereof Download PDFInfo
- Publication number
- CN104103819A CN104103819A CN201310129537.3A CN201310129537A CN104103819A CN 104103819 A CN104103819 A CN 104103819A CN 201310129537 A CN201310129537 A CN 201310129537A CN 104103819 A CN104103819 A CN 104103819A
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon
- carbon compound
- compound
- deoxidation
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/38—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
- H01M4/58—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
-
- 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 the field of lithium battery cathode materials, and provides a silicon-carbon complex. The silicon-carbon complex comprises silicon with the surface subjected to deoxidation processing and a conductive carbon-based buffering agent, and silicon is dispersed in the carbon-based buffering agent. Compared with a silicon-carbon complex prepared from silicon particles with an intrinsic oxide layer, the silicon-carbon complex has better charge/discharge cycle performance and lower first-cycle inreversible capacitance loss. A provided preparation method for the silicon-carbon composite electrode material solves the actual problems that the silicon composite material is high in preparation cost and batch production cannot be realized.
Description
Technical field
The invention belongs to lithium cell cathode material preparation field, relate to a kind of silicon-carbon compound and preparation method thereof.
Background technology
Lithium battery, has energy high, and cyclicity is good, and the life-span is long, and the feature that self-discharge rate is low has substantially replaced the rechargeable battery of other type aspect portable electric appts.In other field, such as electric automobile, the electrical power storage of the unstable energy, lithium ion battery also demonstrates very large potentiality.
Lithium battery is by positive pole, negative pole, and barrier film, and electrolyte forms.Anodal and negative pole is separated by barrier film, positive pole, and negative pole and barrier film are immersed in electrolyte.Positive electrode is generally stratiform transition metal oxide or the phosphate containing lithium.Negative material, carbon active material is widely used, and is generally lamellar graphite or its derivative.When battery charging and discharging, be accompanied by electronics and circulate between two electrodes, itself there is redox reaction in electrode, and lithium ion is embedded into and de-embedding in the stratiform of both positive and negative polarity.Because the centre that is embedded in layer is inlayed and taken off to lithium ion, too large volume does not occur electrode material itself changes, and its structure is preserved, so lithium battery can have the very long life-span.But the final compound forming due to the reaction of graphite and lithium is LiC6, and its a theory gram capacitance is 372mAh/g, the more following lithium battery of high power capacity is not enough for needs for this theoretical capacity.
Silicon is a kind of potential high energy negative material, because its a theory gram capacitance is 4200mAh/g, approximately ten times of graphite, but, but up to the present, silicon is not also successfully applied in lithium battery, one of reason is wherein the oxide on silicon grain surface: SiO2 or SiOx, because silica is not led lithium ion, and silicon dioxide is electronic body, when having stoped the contacting of lithium ion and silicon, stoped again contacting of electronics and silicon, and it also will react with lithium, consume a large amount of lithium ions and form Li2O and less silicon grain.It has limited the current strength discharging and recharging on the one hand like this, it has caused the irreversible loss of capacitance in circulation for the first time on the other hand, reduced energy density and the power density of battery, thereby caused serious problems while using in lithium battery, be difficult to drop into practical.
Summary of the invention
The object of the embodiment of the present invention is to overcome problems of the prior art, and a kind of silicon-carbon compound is provided.
The present invention also provides a kind of method of preparing silicon-carbon compound.
The present invention also provides a kind of cathode of lithium battery active material.
The embodiment of the present invention is achieved in that a kind of silicon-carbon compound, comprises silicon and the conductive carbon based buffer that process through deoxidation on surface, and described silicon is dispersed in carbon back buffer.
The surface of the silicon that preferably, process through deoxidation on described surface is non-oxide compound.
Preferably, the silicon face oxygen content that process through deoxidation on described surface is less than 0.5%.
The superficial layer of the silicon that preferably, process through deoxidation on described surface is hydride.
The superficial layer of the silicon that preferably, process through deoxidation on described surface is carbide or halide.
Preferably, described silicon is at least one in granulated powders and scale like powder.
Preferably, described silicon is one or more in mono-crystalline structures, polycrystalline structure and non crystalline structure.
Preferably, described conductive carbon based buffer is at least one in native graphite, Delanium, unformed carbon black, carbon nano-tube, carbon fiber and Graphene.
A cathode of lithium battery active material, described negative active core-shell material is used silicon-carbon compound to make by coated sintering.
A method of preparing silicon-carbon compound, described method comprises: remove silicon face native oxide layer; Silicon and the conductive carbon based buffer through deoxidation, processed are mixed to form to silicon-carbon compound.
Preferably, described removal silicon face native oxide layer is wet etching deactivation method, comprising: with the native oxide layer on hydrofluoric acid solution erosion removal silicon grain surface, the silicon of unsaturated coordination and hydrogen ion reaction generate si-h bond, form Surface Hydrogen compound layer.
Preferably, described si-h bond reacts with unsaturated compounds and generates silicon-carbon bonds formation carbide lamella.
Preferably, described si-h bond and halogen or halide reaction form halogenation layer.
Preferably, described removal silicon face native oxide layer is dry method reduction deactivation method, comprising: by the native oxide layer of silicon face being reduced to silicon with hydrionic reducibility gas under hot conditions, form si-h bond simultaneously, form Surface Hydrogen compound layer.
In an embodiment of the present invention, there is following technique effect: silicon-carbon compound of the present invention is compared with the silicon-carbon compound by making with the silicon grain of native oxide layer, there is better charge-discharge cycle and the lower irreversible loss of capacitance of first circulation.It is high that the preparation method of silicon-carbon combination electrode material provided by the invention has solved silicon composite preparation cost, the practical problem not can manufacture.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of preparing of silicon-carbon compound of the present invention;
Fig. 2 is Fourier's infrared spectrum of the present invention;
Fig. 3 is TEM video picture comparison diagram of the present invention;
Fig. 4 is charge-discharge performance comparison diagram of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides the method for the silicon-carbon compound that preparation energy density is high.A kind of silicon-carbon compound of the present invention, silicon and the conductive carbon based buffer that process through deoxidation on surface, described silicon is dispersed in carbon back buffer.Silicon-carbon compound of the present invention is compared with the silicon-carbon compound by making with the silicon grain of native oxide layer, has better charge-discharge cycle and the lower irreversible loss of capacitance of first circulation.It is non-oxide compound that the surface of silicon is later processed in deoxidation, and these non-oxide compounds can be hydride, carbide or halide.The present invention is controlled at silicon face oxygen content to be less than 0.5%.Fourier's infrared spectrum as shown in Figure 2.Sample A is the silicon of processing without surperficial deoxidation, and sample B is the silicon that surface is crossed through hydrofluoric acid clean.This two figure that compare, sample A is flexible at 2100cm-1(Si-H) there is no peak, and have very strong SiO-H peak around at 3500cm-1, also there is very strong Si-O at 1000cm-1 simultaneously.Sample B is aobvious is the peak of very weak SiO-H and Si-O, but its Si-H peak (2100cm-1) is very strong.The surface of this explanation silicon is after hydrofluoric acid treatment, and its oxide on surface is eliminated substantially, and outstanding key is saturated by hydrogen.
Equally as shown in Figure 3, without the surface of the silicon of hydrofluoric acid treatment, obviously there is the oxide layer of the several nanometer thickness of one deck, and through the surface of the silicon of hydrofluoric acid treatment, almost there is no oxide layer.
Described silicon is at least one in granulated powders and scale like powder.Described silicon is one or more in mono-crystalline structures, polycrystalline structure and non crystalline structure.Described carbon back buffer is at least one in native graphite, Delanium, unformed carbon black, carbon nano-tube, carbon fiber and Graphene.
Fig. 1 shows the preparation of silicon-carbon compound: first the oxide layer of silicon face is disposed, then the silicon of processing and conductive carbon based buffer are mixed and made into silicon-carbon compound.After making silicon-carbon compound, silicon-carbon compound sintering can be coated and make negative active core-shell material.
The invention provides the method for the silicon-carbon compound that preparation energy density is high.Described method comprises: remove silicon face native oxide layer; Silicon and the conductive carbon based buffer through deoxidation, processed are mixed to form to silicon-carbon compound.
The invention provides two kinds of methods of removing silicon face native oxide layer: wet etching passivation and dry method reduction passivation.
Wet etching deactivation method is under the condition of room temperature or heating a little, removes the native oxide layer of silicon face with hydrofluoric acid solution corrosion, and the silicon of unsaturated coordination and hydrogen ion reaction generate si-h bond, form Surface Hydrogen compound layer.In specific embodiment, the si-h bond of silicon face can also react with unsaturated compounds and generate silicon-carbon bonds formation carbide lamella; Si-h bond also can form halide layer with halogen or halide reaction.
Dry method reduction deactivation method is with being with hydrionic reducibility gas, as hydrogen is reduced to silicon by the native oxide layer of silicon face under hot conditions, forms si-h bond protection silicon face simultaneously.
The present invention can be coated this silicon-carbon compound to be sintered to active material, and is prepared as cathode of lithium battery.
Charge-discharge performance comparison diagram as shown in Figure 4, be using surface through and the composite material that is not active material through the acid-treated silicon of hydrogen fluorine (HF) as the charge-discharge performance comparison of the lithium ion battery of negative pole.As can be seen from the figure the aspects such as irreversible loss of capacitance of the composite negative pole of the silicon of surface process hydrofluoric acid treatment in charge-discharge cycle and circulation for the first time, compares and does not have treated silicon composite cathode, all has greatly improved.
With reference to the following example more detailed description each aspect of the present invention.The following example is only for illustrative object, and is not intended to limit the scope of total inventive concept.
Embodiment 1:
The present embodiment is for adopting the silicon of wet method removal surface oxide layer to make Si-C composite material.
The silicon grain of 2.0 grams is mixed with the hydrofluoric acid solution of 500 milliliter 2.5%, under room temperature, stir ten minutes, then filter, by deionized water cleaning and filtering repeatedly, until filtrate is neutral.
The graphene oxide of getting 5 grams mixes with the silica flour of 100 nanometers of 2.5 grams of processing through hydrofluoric acid deoxidation, stirring at room 12 hours.Get 75 milliliters of sugared alcoholic solutions (1.5 grams) and sneak into the mixture of nano-silicon, stir 2 hours, 80 ℃ of oven dry, gained mixture under argon atmosphere, sintering 6h at 1100 temperature.
Embodiment 2:
Compare with embodiment 1, difference is: with organic polymer, be not limited to PEO, replace sugar as the coated initiation material of carbon.
Embodiment 3:
This embodiment is for adopting the oxide layer of dry method reduction silicon face to generate silicon hydrogen meter surface layer.This process conventionally and the coated secondary granulation process combination of composite material.
The suspension of the silicon grain of 2.5 gram of 100 nanometer and 5 grams of expanded graphite alkene mixes, and at room temperature stirs 28 hours, filters, and cleans, dry.Again with 75 milliliters, gained composite material, containing 1.5 grams of sugared aqueous solution, stirs, and makes pasty state batch mixing.This batch mixing is placed in tube furnace; under the protection of inert gas argon gas; be heated to 80 degrees Celsius, be incubated after 1 hour, be warmed up to 400 degrees Celsius; after cracking 3 hours; change hydrogen/argon gas mist (H2 accounts for 10%, volume) into, be warmed up to 1100 degrees Celsius; after sintering 6 hours, naturally cool to room temperature.
Embodiment 4:
This embodiment is by wet method (embodiment 1) and dry method (embodiment 3) combination.The silicon of usining through wet treatment is as initial silicon materials, silicon and Graphene or its oxide are made after composite material, with organic substance under the atmosphere of argon gas/hydrogen gas mixture, sintering 6h at 1100 temperature.
The present invention can be coated this silicon-carbon compound to be sintered to active material, and is prepared as cathode of lithium battery:
With the coated silicon-carbon compound of preparation and another standby carbon-based conductive agent, mix, after ball milling, sneak into the solution of marine alga binder, stir into slurry.This slurry is coated on Copper Foil equably, dries.Using the electrode of preparation as positive pole, and lithium sheet metal, as negative pole, separates both positive and negative polarity with barrier film, injects electrolyte, makes lithium battery.Discharging and recharging stopping potential is 0.02 volt to 1.5 volts, and charging or discharging current is 0.1 milliampere.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (14)
1. a silicon-carbon compound, is characterized in that, comprises silicon and the conductive carbon based buffer that process through deoxidation on surface, and described silicon is dispersed in carbon back buffer.
2. silicon-carbon compound as claimed in claim 1, is characterized in that, the surface of the silicon that process through deoxidation on described surface is non-oxide compound.
3. silicon-carbon compound as claimed in claim 2, is characterized in that, the silicon face oxygen content that process through deoxidation on described surface is less than 0.5%.
4. silicon-carbon compound as claimed in claim 2, is characterized in that, the superficial layer of the silicon that process through deoxidation on described surface is hydride.
5. silicon-carbon compound as claimed in claim 2, is characterized in that, the superficial layer of the silicon that process through deoxidation on described surface is carbide or halide.
6. silicon-carbon compound as claimed in claim 1, is characterized in that, described silicon is at least one in granulated powders and scale like powder.
7. silicon-carbon compound as claimed in claim 1, is characterized in that, described silicon is one or more in mono-crystalline structures, polycrystalline structure and non crystalline structure.
8. silicon-carbon compound as claimed in claim 1, is characterized in that, described conductive carbon based buffer is at least one in native graphite, Delanium, unformed carbon black, carbon nano-tube, carbon fiber and Graphene.
9. a cathode of lithium battery active material, is characterized in that, described negative active core-shell material is used silicon-carbon compound as claimed in claim 1 to make by coated sintering.
10. a method of preparing silicon-carbon compound, is characterized in that, described method comprises: remove silicon face native oxide layer; Silicon and the conductive carbon based buffer through deoxidation, processed are mixed to form to silicon-carbon compound.
11. methods as claimed in claim 10, it is characterized in that, described removal silicon face native oxide layer is wet etching deactivation method, comprise: with the native oxide layer on hydrofluoric acid solution erosion removal silicon grain surface, the silicon of unsaturated coordination and hydrogen ion reaction generate si-h bond, form Surface Hydrogen compound layer.
12. methods as claimed in claim 11, is characterized in that, described method further comprises: described si-h bond reacts with unsaturated compounds and generates silicon-carbon bonds formation carbide lamella.
13. methods as claimed in claim 11, is characterized in that, described method further comprises: described si-h bond and halogen or halide reaction form halogenation layer.
14. methods as claimed in claim 10, it is characterized in that, described removal silicon face native oxide layer is dry method reduction deactivation method, comprise: by the native oxide layer of silicon face being reduced to silicon with hydrionic reducibility gas under hot conditions, form si-h bond simultaneously, form Surface Hydrogen compound layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310129537.3A CN104103819A (en) | 2013-04-15 | 2013-04-15 | Silicon-carbon complex and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310129537.3A CN104103819A (en) | 2013-04-15 | 2013-04-15 | Silicon-carbon complex and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104103819A true CN104103819A (en) | 2014-10-15 |
Family
ID=51671774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310129537.3A Pending CN104103819A (en) | 2013-04-15 | 2013-04-15 | Silicon-carbon complex and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104103819A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332613A (en) * | 2014-11-18 | 2015-02-04 | 东莞市翔丰华电池材料有限公司 | Lithium ion battery silicon-carbon composite negative material and its preparation method |
| CN106025243A (en) * | 2016-07-29 | 2016-10-12 | 成都新柯力化工科技有限公司 | Silicon negative electrode composite material for lithium-ion battery and preparation method thereof |
| CN112599747A (en) * | 2020-12-16 | 2021-04-02 | 德翼高科(杭州)科技有限公司 | Preparation method of carbon nano tube/silicon composite material |
| WO2022215498A1 (en) * | 2021-04-08 | 2022-10-13 | 三菱マテリアル株式会社 | Negative-electrode material, battery, method for producing negative-electrode material, and method for producing battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719543A (en) * | 2009-09-30 | 2010-06-02 | 清华大学 | Method for preparing silicon nanowire array membrane electrode |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| CN102969488A (en) * | 2012-12-05 | 2013-03-13 | 奇瑞汽车股份有限公司 | Amorphous porous silicon, preparation method of amorphous porous silicon, and lithium ion battery containing amorphous porous silicon |
-
2013
- 2013-04-15 CN CN201310129537.3A patent/CN104103819A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101719543A (en) * | 2009-09-30 | 2010-06-02 | 清华大学 | Method for preparing silicon nanowire array membrane electrode |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| CN102969488A (en) * | 2012-12-05 | 2013-03-13 | 奇瑞汽车股份有限公司 | Amorphous porous silicon, preparation method of amorphous porous silicon, and lithium ion battery containing amorphous porous silicon |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332613A (en) * | 2014-11-18 | 2015-02-04 | 东莞市翔丰华电池材料有限公司 | Lithium ion battery silicon-carbon composite negative material and its preparation method |
| CN106025243A (en) * | 2016-07-29 | 2016-10-12 | 成都新柯力化工科技有限公司 | Silicon negative electrode composite material for lithium-ion battery and preparation method thereof |
| CN106025243B (en) * | 2016-07-29 | 2018-02-09 | 成都新柯力化工科技有限公司 | A kind of lithium ion battery silicon anode material and preparation method thereof |
| CN112599747A (en) * | 2020-12-16 | 2021-04-02 | 德翼高科(杭州)科技有限公司 | Preparation method of carbon nano tube/silicon composite material |
| WO2022215498A1 (en) * | 2021-04-08 | 2022-10-13 | 三菱マテリアル株式会社 | Negative-electrode material, battery, method for producing negative-electrode material, and method for producing battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107507972B (en) | Preparation method of silicon-carbon negative electrode material, silicon-carbon negative electrode material and lithium ion battery | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| EP3352251A1 (en) | Method for preparing silicon-carbon composite, negative electrode, and lithium ion battery | |
| CN102332571B (en) | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece | |
| CN100401559C (en) | Preparation method for composite negative electrode material of lithium ion battery | |
| WO2017024720A1 (en) | Preparation method for high capacity lithium-ion battery negative electrode material | |
| CN106025211A (en) | Preparation method of high-capacity silicon-based negative electrode material of lithium-ion battery | |
| CN103326023A (en) | High-performance lithium ion battery silicon-carbon cathode material and preparation method thereof | |
| JP5246538B2 (en) | All-solid battery, method for producing all-solid battery, and method for imparting electronic conductivity | |
| CN104538607A (en) | Preparation method of silicon-carbon negative electrode material for lithium ion battery | |
| CN104319401A (en) | Anode material for double-shell capsule-shaped silicon-based lithium-ion battery and preparation method of anode material | |
| CN106532010B (en) | Silicon-silicon nitride-carbon composite material and preparation method and application method thereof | |
| CN104993174A (en) | Preparation method of material of negative electrode of lithium ion battery | |
| CN102610814B (en) | Composite nano-structure carbon-layer-cladded lithium iron phosphate electrode material and preparation method thereof | |
| CN113690429A (en) | Carbon-coated graphene/metal oxide composite material and preparation method thereof | |
| CN110380029B (en) | Silicon-based negative electrode material for lithium battery and preparation method thereof | |
| CN108923027B (en) | Organic acid modified Si/TiO2Negative electrode material of/rGO @ C lithium ion battery and preparation method and application thereof | |
| CN108091866B (en) | Preparation method of silicon-carbon negative electrode material for lithium ion battery | |
| CN105280901B (en) | The preparation method of spherical porous silicon carbide composite particles | |
| CN104103819A (en) | Silicon-carbon complex and preparation method thereof | |
| CN106887591B (en) | Composite conductive agent for lithium ion battery and preparation method thereof | |
| CN112234186A (en) | MXene nanodot coated modified lithium ion battery cathode material and preparation method thereof | |
| CN116706013A (en) | Composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN103887477B (en) | A kind of preparation method of the Graphene modified phosphate ferrum lithium anode material of high power capacity | |
| WO2023016047A1 (en) | Negative electrode material and preparation method therefor, lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20141015 |