CN104979559A - Nano-copper coated porous nano silicon composite material as well as preparation method and application thereof - Google Patents
Nano-copper coated porous nano silicon composite material as well as preparation method and application thereof Download PDFInfo
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- CN104979559A CN104979559A CN201410133908.XA CN201410133908A CN104979559A CN 104979559 A CN104979559 A CN 104979559A CN 201410133908 A CN201410133908 A CN 201410133908A CN 104979559 A CN104979559 A CN 104979559A
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Abstract
The invention discloses a nano-copper coated porous nano silicon composite material as well as a preparation method and application thereof. The method comprises the following steps: (1) performing activating pretreatment on a porous nano silicon powder material prepared from an acid etching silicon allay; and (2) dispersing the porous nano silicon powder material after being subjected to activating pretreatment in an electroless copper plating solution, performing electroless copper plating, filtering, washing and drying so as to obtain the nano-copper coated porous nano silicon composite material. As being used as a negative material of a lithium ion battery, the nano-copper coated porous nano silicon composite material provided by the invention has very high specific discharge capacity, charge-discharge cycling stability and excellent charge-discharge power characteristic; the specific discharge capacity of the material used as a negative material is far higher than that of a graphite negative material in an existing lithium ion battery; as the cost of preparation of porous nano silicon powder and the cost of electroless copper plating are low, the preparation method of the material is simple and easy to operate, the low-cost continuous and large-scale production is realized, and the method is suitable for being used in the production of a new-generation high-performance lithium ion battery silicon negative material.
Description
Technical field
The invention belongs to chemical energy storage field, be specifically related to a kind of lithium ion battery negative material: the coated porous silicon composite of Nanometer Copper.This material is the porous silicon generated with acid etch silicon alloy, and then chemical plating Nanometer Copper and making.Because this material has very high specific discharge capacity, charge and discharge cycles stability and outstanding charge-discharge electric power characteristic, can be used for preparing high-performance lithium ion battery, for electric motor car and novel portable electronic appliance and mobile phone, iPad etc.
Background technology
Chemical power source is a kind of device of electric energy by chemical energy.Secondary cell can store electrical energy Reusability, but also can store the electric energy transformed by luminous energy, wind energy etc.Secondary cell common in the market has: lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery etc.In recent years, the indices (environmental protection, high energy etc.) of portable electric appts to energy storage device is more and more higher.The development of electric motor car more needs the secondary cell of high-energy-density.Lithium ion battery is latest generation secondary cell, have that energy density is high, operating voltage is high, charging rate is fast, have extended cycle life, self discharge minimum (5%), environmental friendliness, safety and stability feature performance benefit, the requirement of above environmental protection, high energy can be met well.Therefore the research of various countries researcher to high-energy-density and high power density lithium ion battery is greatly facilitated.Due to the theoretical specific capacity lower (372 mAh/g) of graphite as anode material for lithium-ion battery practical at present, develop the focus that the new negative material with height ratio capacity becomes research and development.In recent years, silicon materials are subject to extensive concern because of the theoretical specific capacity (4200mAh/g) of its superelevation.But the shortcoming of the violent bulk effect occurred during its discharge and recharge and low conductivity hinders the practical of silicon.In order to overcome the shortcoming that silicon expands (can triploid amass) when charging and lithium diffusion coefficient in silicon is little, research both domestic and external mainly adopts the methods such as nano-silicon, nano wire, nanotube, mesoporous silicon and ultra-thin silicon layer.Also the report adopting chemical vapour deposition technique in conjunction with magnetron sputtering method synthesis Si/ metal (Ag, Sn, Co, Cu) compound is had, to improve materials conductive rate.But these method costs are high, complex process, not easily produces in a large number.Chinese patent (the application number: the nano-silicon negative material 201310122811.4) proposing a kind of novel porous structure, solves the problem of the bulk effect of silicon well of application before us.Current focus is the specific discharge capacity improving silicon materials, and power-performance.The present invention is on this basis, Bian electroless copper method is carried out Na meter Copper to the nano-silicon of above-mentioned loose structure and is cladded, and has obtained the coated porous nanometer silicon composite material of Nanometer Copper with high specific discharge capacity, high charge-discharge cyclical stability and outstanding charge-discharge electric power performance.
Summary of the invention
The object of this invention is to provide a kind of high performance lithium ion battery negative material and production method thereof, utilize the method for electroless copper clad nano copper on the porous nano silicon grain obtained with acid etching silicon alloy.The coated porous nano silica fume of the method gained Nanometer Copper has very high specific discharge capacity, charge and discharge cycles stability and outstanding charge-discharge electric power characteristic.
For achieving the above object, the invention provides the preparation method of the coated porous nanometer silicon composite material of a kind of Nanometer Copper, the method comprises following concrete steps:
Step 1, carries out activating pretreatment to porous nano Si powder material;
Step 2, by the porous nano Si powder dispersion of materials after activating pretreatment in chemical copper plating solution, carries out electroless copper to it, then, can obtain the coated porous nano silicon composite of Nanometer Copper after filtration, washing, oven dry.
The preparation method of above-mentioned Nanometer Copper coated porous silicium cathode material porous nano Si powder used; wherein; described porous nano silicon materials select nano-silicon particulate or silica fibre; the particle diameter of nano-silicon particulate is 5-600nm; the diameter of silica fibre is 5-700nm; length is 10nm-100 μm, and specific area is 10-400m
2/ g.
The preparation method of the coated porous nanometer silicon composite material of above-mentioned Nanometer Copper, wherein, described porous nano Si powder is prepared by acid etching silicon alloy powder, and described silicon alloy refers to the alloy powders such as sial, silicon magnesium or ferrosilicon, and in this silicon alloy, the weight content of silicon is 3-95%.
The preparation method of the coated porous nanometer silicon composite material of above-mentioned Nanometer Copper, wherein, described activating pretreatment refers to: after above-mentioned porous nano Si powder and zinc or tin metal powder mixing, be dispersed in activating solution, slow stirring is until porous nano silicon grain surface produces avtive spot Ag simple substance, complete activation, described activating solution composition: 0.1 ~ 20gL
-1silver ammino solution or liquor argenti nitratis ophthalmicus.
The preparation method of the coated porous nanometer silicon composite material of above-mentioned Nanometer Copper, wherein, described activating pretreatment refers to: above-mentioned porous nano Si powder, be dispersed in activating solution, slow stirring also adds reducing agent, until particle surface produces avtive spot Ag simple substance, complete activation, described activating solution composition: 0.1 ~ 20gL
-1silver ammino solution or liquor argenti nitratis ophthalmicus; The consumption of described reducing agent is to make silver-colored ammonia or silver nitrate Restore All become the 1-1.5 of the consumption of Ag doubly; More than any one in glucose, hydrazine sulfate, hydrazine hydrate or sodium borohydride selected by described reducing agent.
The preparation method of the coated porous nanometer silicon composite material of above-mentioned Nanometer Copper, wherein, described chemical copper plating solution is composed as follows: CuCl
2or CuSO
4: 1 ~ 20gL
-1, sodium potassium tartrate tetrahydrate: 10 ~ 200gL
-1; Any one in Ci Ya Lin Suan Na, diglycolic acid, borine or formaldehyde: 1 ~ 40mLL
-1.
Present invention also offers a kind of coated porous nanometer silicon composite material of Nanometer Copper prepared according to said method, wherein, this composite material comprises porous nano silicon, be coated with Metal copper nanoparticles at this porous nano silicon face or there is the copper-clad coating of nano thickness, wherein, the particle diameter of copper particulate is 1nm-300nm; In copper clad porous nano silicon composite, the content of copper is 0.1-70%, and the specific area of this composite material is 10-450m
2/ g.
Present invention also offers the purposes of the coated porous nanometer silicon composite material of a kind of above-mentioned Nanometer Copper, the coated porous nanometer silicon composite material of this Nanometer Copper is used as the silicium cathode active material of lithium ion battery, made silicium cathode is made up of the coated porous silicon composite of Nanometer Copper, electrically conductive graphite or charcoal, aqueous systems or organic solvent system binding agent, wherein each composition weight content (accounting for the ratio of all cathode sizes) is: the coated porous silicon 10 ~ 95% of Nanometer Copper, electrically conductive graphite or charcoal 1 ~ 80%, binding agent 1 ~ 40%, the substrate copper thickness of electrode is 5 ~ 60 μm.
Above-mentioned purposes, wherein, described aqueous systems high polymer binder is at least 2 kinds in sodium carboxymethylcellulose pyce, styrene butadiene rubbers, polyacrylate based terpolymers latex, acrylonitrile multiple copolymer, and the binding agent of organic solvent system is Kynoar.
Above-mentioned purposes, wherein, the electrolyte of described lithium ion battery is made up of lithium salts, electrolysis additive and mixed organic solvents; Described lithium salts is LiPF
6its concentration is 0.3-2mol/L, described mixed organic solvents is made up of at least 2 kinds in ethylene carbonate, diethyl carbonate, dimethyl carbonate, propene carbonate, carbonic acid first butyl ester, ethyl propyl carbonic acid ester, dibutyl carbonate, diglycol ethylene dimethyl ether, contracting TRIGLYME, and often kind of weight of solvent accounts for the gross weight <90% of mixed organic solvents; Described electrolysis additive is the mixture of any one or any two kinds in fluorinated ethylene carbonate, vinylene carbonate, trithiocarbonic acid vinylene, and its concentration is 0.05%-30wt%.
The coated porous nanometer silicon composite material of Nanometer Copper provided by the invention; existence due to nano copper particle improves the conductivity of porous silica material; overcome the shortcoming that the electronic conductivity of silicon own is low; and nano copper particle or Nanometer Copper tectal existence reunion when can stop charging between silicon grain; thus obtain very high specific discharge capacity, charge and discharge cycles stability and outstanding charge-discharge electric power characteristic.Porous nano silica flour used is made up of acid etch silicon alloy powder, has high porosity, the expansion of silicon materials during to hold charging.And, due to the preparation of porous nano silica flour with electroless copper method cost is low, method simply, easily operates, be applicable to large-scale production, can be used as the silicium cathode material of high performance lithium ion battery.
The present invention makes public for the first time copper clad porous nano silicon composite and preparation method thereof, the coated porous nanometer silicon composite material of this Nanometer Copper is used as negative pole in lithium-ion battery electrolytes, demonstrates very high specific discharge capacity and charge and discharge cycles stability, and outstanding charge-discharge electric power performance.The preparation method of this copper clad porous nano silicon composite is simple, and cost is lower, is easy to a large amount of production; Be applicable to the need of production of high performance lithium ion battery.
Accompanying drawing explanation
Fig. 1 a is the scanning electron microscope (SEM) photograph of the porous nano silicon composite that Nanometer Copper of the present invention is modified; Fig. 1 b is the partial enlarged drawing of the scanning electron microscope (SEM) photograph of the porous nano silicon composite that Nanometer Copper of the present invention is modified.
Fig. 2 is charge and discharge cycles discharge capacity and the efficiency for charge-discharge figure of battery CR2025 provided by the invention.
Fig. 3 is battery CR2025 provided by the invention with the result figure of various current density charge and discharge cycles stage by stage.
Embodiment
Below by embodiment, the present invention is described in detail, example is below the example of technology contents according to the invention, do not illustrate that the present invention is only limitted to the content described in following example, those of skill in the art all belong to content of the present invention according to the product of the claims in the present invention item or the only simple replacement manufacture of do.
The preparation method of porous nano Si powder of the present invention is as follows: the silicon alloy (composition: the silicon content of silicon alloy powder is that mass percent counts 3% to 95% taking certain mass, powder diameter: 0.01 μm-50 μm, can be silicon magnesium, sial or Antaciron powder), add excessive HCl in batches, or H
2sO
4in (analyzing pure) aqueous solution (percent mass Particle density 0.1%-30%), and constantly stir with magnetic stirring apparatus.Product through washed with de-ionized water repeatedly.Then be placed in HF solution (percent mass Particle density 0.5%-10%) to stir several hours, with the SiO on dissolves silicon surface
2.Use deionized water, absolute ethanol washing respectively repeatedly again.Finally be placed in vacuum drying oven, dry at 80 DEG C, obtain porous nano Si powder.
Embodiment
First, the porous nano Si powder prepared by above-mentioned employing aciding, adopts electroless copper method at porous Si copper coating, prepares the coated porous nanometer silicon composite material of Nanometer Copper.Preparation process is as follows: activating pretreatment, and under ultrasound condition, the porous nano Si powder prepared by aciding and metal dust, after zinc or tin metal powder mixing, be dispersed in 0.1 ~ 20gL
-1in silver ammino solution or liquor argenti nitratis ophthalmicus activating solution, slow stirring is until porous nano silicon grain surface produces avtive spot Ag simple substance, complete activation, to increase active surface, this step guarantees the hydrophily of Si particle surface, suitable roughness and good coating adhesion; Then, porous Si powder good for activating pretreatment is carried out electroless copper.Again after filtration, wash and dry the porous nano Si composite material that can obtain copper and modify.In the porous nano Si composite material that this copper is modified, the diameter of silica fibre is about 50 nanometers, and on it, the particle diameter of the Cu particulate of deposition is about 5-10nm.The scanning electron microscope (SEM) photograph of the porous Si composite material that copper is modified is shown in Fig. 1 a, 1b.Wherein, 1a is the scanning electron microscope (SEM) photograph of the porous Si composites that Nanometer Copper is modified, and Fig. 1 b is the scanning electron microscope (SEM) photograph of the porous Si composite material partial enlargement that Nanometer Copper is modified.
Porous Si electrode is by the coated porous nanometer silicon composite material of active material Nanometer Copper: conductive carbon black (super P): form with water-soluble glue (sodium carboxymethylcellulose pyce+water system butadiene-styrene rubber)=7:1.5:1.5.The cathode size mixed (the coated porous nanometer silicon composite material of Nanometer Copper, conductive carbon black and water-soluble glue form cathode size) is coated on Copper Foil.After 80 DEG C, vacuum is dried, pole piece is washed into the disk of 14mm, each disk contains active material (i.e. the coated porous nanometer silicon composite material of Nanometer Copper) and is about 1.5mg.Be assembled into button cell (CR2025), Bian organic electrolyte carries out constant current charge-discharge test on the discharge and recharge instrument system of Land Instrument Ltd..Discharge and recharge electricity current density is 200mA/g.Electrode discharge is steady, and discharge platform is similar to graphite electrode.Fig. 2 is charge and discharge cycles discharge capacity and the efficiency for charge-discharge figure of this battery CR2025.After the coated porous nano-silicon electrode cycle of Nanometer Copper 150 times, still Absorbable organic halogens is at more than 1600mAh/g for specific discharge capacity, and efficiency for charge-discharge is 99%.Demonstrate very high specific discharge capacity and outstanding cyclical stability.Fig. 3 is with the result of various current density charge and discharge cycles stage by stage.Each stage discharge and recharge 11 times.As seen from Figure 3, electrode can in discharge and recharge under higher current density.Under 1A/g, specific discharge capacity still can be had to be about 1200mAh/g.This lithium ion cell nano copper clad porous nano silicium cathode material has very high specific discharge capacity, charge and discharge cycles stability, and outstanding charge-discharge electric power performance.And preparation method's cost is low, simple to operate, easily a large amount of production, the very potential negative active core-shell material becoming the lithium ion battery of the practical high-energy-density of a new generation.
In preferred embodiments more of the present invention, described porous nano silicon materials select nano-silicon particulate or silica fibre, and the particle diameter of nano-silicon particulate is 5-600nm, and the diameter of silica fibre is 5-700nm, and length is 10nm-100 μm, and specific area is 10-400m
2/ g.
In preferred embodiments more of the present invention, described activating pretreatment refers to: above-mentioned porous nano Si powder, be dispersed in activating solution, slow stirring also adds zinc or tin metal powder, until particle surface produces avtive spot Ag simple substance, complete activation, described activating solution composition: 0.1 ~ 20gL
-1silver ammino solution or liquor argenti nitratis ophthalmicus.
In preferred embodiments more of the present invention, described activating pretreatment refers to: above-mentioned porous nano Si powder, be dispersed in activating solution, slow stirring also adds any one in glucose, hydrazine sulfate, hydrazine hydrate or sodium borohydride as reducing agent, until particle surface produces avtive spot Ag simple substance, complete activation, described activating solution composition: 0.1 ~ 20gL
-1silver ammino solution or liquor argenti nitratis ophthalmicus.
In preferred embodiments more of the present invention, described electroless copper chemical plating fluid used is composed as follows: CuSO
4: 1 ~ 20gL
-1, sodium potassium tartrate tetrahydrate: 10 ~ 200gL
-1, diglycolic acid: 1 ~ 40mLL
-1.
In preferred embodiments more of the present invention, provide a kind of silicium cathode being made the lithium ion battery of active material by the coated porous nanometer silicon composite material of above-mentioned Nanometer Copper.This silicium cathode is made up of the coated porous nano silicon material of Nanometer Copper, electrically conductive graphite or charcoal, aqueous systems or organic solvent system binding agent.Wherein each composition weight content is: the coated porous nano-silicon 10 ~ 95% of Nanometer Copper, electrically conductive graphite or charcoal 1 ~ 80%, and binding agent 1 ~ 40%, substrate copper thickness is 5 ~ 60 μm.
Further, in more excellent embodiment, described binding agent is at least 2 kinds in sodium carboxymethylcellulose pyce, styrene butadiene rubbers, polyacrylate based terpolymers latex, acrylonitrile multiple copolymer, and the binding agent of described organic solvent system is Kynoar.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a preparation method for the coated porous nanometer silicon composite material of Nanometer Copper, is characterized in that, the method comprises following concrete steps:
Step 1, carries out activating pretreatment to porous nano Si powder material;
Step 2, by the porous nano Si powder dispersion of materials after activating pretreatment in chemical copper plating solution, carries out electroless copper to it, then, can obtain the coated porous nano silicon composite of Nanometer Copper after filtration, washing, oven dry.
2. the preparation method of the coated porous nanometer silicon composite material of Nanometer Copper as claimed in claim 1; it is characterized in that; described porous nano silicon materials select nano-silicon particulate or silica fibre; the particle diameter of nano-silicon particulate is 5-600nm; the diameter of silica fibre is 5-700nm; length is 10nm-100 μm, and specific area is 10-400m
2/ g.
3. the preparation method of the coated porous nanometer silicon composite material of Nanometer Copper as claimed in claim 1 or 2, it is characterized in that, described porous nano Si powder is prepared by acid etch silicon alloy powder, described silicon alloy select in silicon magnesium, sial or ferrosilicon any one, and silicon weight content is 3-95% in this silicon alloy.
4. the preparation method of the coated porous nanometer silicon composite material of Nanometer Copper as claimed in claim 1, it is characterized in that, described activating pretreatment refers to: after above-mentioned porous nano Si powder and zinc or tin metal powder mixing, be dispersed in activating solution, slow stirring is until porous nano silicon grain surface produces avtive spot Ag simple substance, complete activation, described activating solution composition: 0.1 ~ 20gL
-1silver ammino solution or liquor argenti nitratis ophthalmicus.
5. the preparation method of the coated porous nanometer silicon composite material of Nanometer Copper as claimed in claim 1, it is characterized in that, described activating pretreatment refers to: above-mentioned porous nano Si powder, be dispersed in activating solution, slow stirring also adds reducing agent, until particle surface produces avtive spot Ag simple substance, complete activation, described activating solution composition: 0.1 ~ 20gL
-1silver ammino solution or liquor argenti nitratis ophthalmicus; The consumption of described reducing agent is to make silver-colored ammonia or silver nitrate Restore All become the 1-1.5 of the consumption of Ag doubly; More than any one in glucose, hydrazine sulfate, hydrazine hydrate or sodium borohydride selected by described reducing agent.
6. the preparation method of the coated porous nanometer silicon composite material of Nanometer Copper as claimed in claim 1, it is characterized in that, described chemical copper plating solution is composed as follows: CuCl
2or CuSO
4: 1 ~ 20gL
-1, sodium potassium tartrate tetrahydrate: 10 ~ 200gL
-1; Any one in Ci Ya Lin Suan Na, diglycolic acid, borine or formaldehyde: 1 ~ 40mLL
-1.
7. the coated porous nanometer silicon composite material of Nanometer Copper adopting the method in claim 1 or 2 or 4-6 described in any one to prepare, it is characterized in that, this composite material comprises porous nano silicon, be coated with Metal copper nanoparticles at this porous nano silicon face or there is the copper-clad coating of nano thickness, wherein, the particle diameter of copper particulate is 1nm-300nm; In copper clad porous nano silicon composite, the content of copper is 0.1-70%, and the specific area of this composite material is 10-450m
2/ g.
8. the purposes of the coated porous nanometer silicon composite material of Nanometer Copper according to claim 7, it is characterized in that, the coated porous nanometer silicon composite material of this Nanometer Copper is used as the silicium cathode active material of lithium ion battery, described silicium cathode is made up of the coated porous silicon composite of Nanometer Copper, electrically conductive graphite or charcoal, aqueous systems or organic solvent system binding agent, wherein each composition weight content is: the coated porous silicon 10 ~ 95% of Nanometer Copper, electrically conductive graphite or charcoal 1 ~ 80%, binding agent 1 ~ 40%, the substrate copper thickness of electrode is 5 ~ 60 μm.
9. purposes as claimed in claim 8, it is characterized in that, described aqueous systems high polymer binder is at least 2 kinds in sodium carboxymethylcellulose pyce, styrene butadiene rubbers, polyacrylate based terpolymers latex, acrylonitrile multiple copolymer, and the binding agent of organic solvent system is Kynoar.
10. purposes as claimed in claim 8, it is characterized in that, the electrolyte of described lithium ion battery is made up of lithium salts, electrolysis additive and mixed organic solvents; Described lithium salts is LiPF
6its concentration is 0.3-2mol/L, described mixed organic solvents is made up of at least 2 kinds in ethylene carbonate, diethyl carbonate, dimethyl carbonate, propene carbonate, carbonic acid first butyl ester, ethyl propyl carbonic acid ester, dibutyl carbonate, diglycol ethylene dimethyl ether, contracting TRIGLYME, and often kind of weight of solvent accounts for the gross weight <90% of mixed organic solvents; Described electrolysis additive is any one or any two kinds in fluorinated ethylene carbonate, vinylene carbonate, trithiocarbonic acid vinylene, and its concentration is 0.05%-30wt%.
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| CN105655558A (en) * | 2016-01-19 | 2016-06-08 | 天津理工大学 | Preparation method and application of AlCuFe quasi-crystal alloy coated with metal film |
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| CN107394150A (en) * | 2017-07-14 | 2017-11-24 | 东南大学 | A kind of mesoporous silicon copper composition electrode material and its preparation method and application |
| CN107492651A (en) * | 2017-09-05 | 2017-12-19 | 中国科学院物理研究所 | A kind of nano-silicon negative material of double-coating and its preparation method and application |
| CN107623121A (en) * | 2017-10-18 | 2018-01-23 | 山东大学 | A kind of metallic cover porous silicon composite electrode material and preparation method thereof |
| CN107785095A (en) * | 2017-10-27 | 2018-03-09 | 江苏时瑞电子科技有限公司 | A kind of porous silicon electrocondution slurry of copper doped and graphene and preparation method thereof |
| WO2019047010A1 (en) * | 2017-09-05 | 2019-03-14 | 中国科学院物理研究所 | Double layer-coated nano-silicon negative electrode material, preparation method therefor and use thereof |
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| CN105655558A (en) * | 2016-01-19 | 2016-06-08 | 天津理工大学 | Preparation method and application of AlCuFe quasi-crystal alloy coated with metal film |
| CN106784613A (en) * | 2017-02-23 | 2017-05-31 | 华南理工大学 | A kind of porous silicon copper-plating electrode for lithium ion battery and preparation method thereof |
| CN107394150A (en) * | 2017-07-14 | 2017-11-24 | 东南大学 | A kind of mesoporous silicon copper composition electrode material and its preparation method and application |
| WO2019047010A1 (en) * | 2017-09-05 | 2019-03-14 | 中国科学院物理研究所 | Double layer-coated nano-silicon negative electrode material, preparation method therefor and use thereof |
| CN107492651A (en) * | 2017-09-05 | 2017-12-19 | 中国科学院物理研究所 | A kind of nano-silicon negative material of double-coating and its preparation method and application |
| US11362327B2 (en) | 2017-09-05 | 2022-06-14 | Institute Of Physics, Chinese Academy Of Sciences | Double layer-coated nano-silicon negative electrode material, a method for preparing the same and use thereof |
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| CN107623121A (en) * | 2017-10-18 | 2018-01-23 | 山东大学 | A kind of metallic cover porous silicon composite electrode material and preparation method thereof |
| CN107623121B (en) * | 2017-10-18 | 2019-12-27 | 山东大学 | Metal-coated porous silicon composite electrode material and preparation method thereof |
| CN107785095A (en) * | 2017-10-27 | 2018-03-09 | 江苏时瑞电子科技有限公司 | A kind of porous silicon electrocondution slurry of copper doped and graphene and preparation method thereof |
| WO2019114373A1 (en) * | 2017-12-12 | 2019-06-20 | 中国科学院物理研究所 | Composite-coated nano-tin negative electrode material, preparation method therefor and use thereof |
| US11362328B2 (en) | 2017-12-12 | 2022-06-14 | Institute Of Physics, Chinese Academy Of Sciences | Composite-coated nano-tin negative electrode material and preparation method and use thereof |
| CN113454251A (en) * | 2018-12-18 | 2021-09-28 | 赛莫必乐公司 | Large area copper nanofoam with layered structure for use as an electrode |
| CN109686942A (en) * | 2018-12-21 | 2019-04-26 | 东北大学 | A kind of preparation method of silicon based anode material |
| CN110993899B (en) * | 2019-10-14 | 2020-10-30 | 浙江大学 | Nano-copper particle modified micron-sized porous silicon composite material and preparation method thereof |
| CN110993899A (en) * | 2019-10-14 | 2020-04-10 | 浙江大学 | Nano-copper particle in-situ modified micron-sized porous silicon composite structure material and preparation method thereof |
| CN114709390A (en) * | 2022-04-01 | 2022-07-05 | 蔚来汽车科技(安徽)有限公司 | Silicon anode material, secondary battery and device |
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