CN102130329A - Preparation method of lithium ion battery film cathode containing porous polymer elastomer - Google Patents
Preparation method of lithium ion battery film cathode containing porous polymer elastomer Download PDFInfo
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- CN102130329A CN102130329A CN2011100368541A CN201110036854A CN102130329A CN 102130329 A CN102130329 A CN 102130329A CN 2011100368541 A CN2011100368541 A CN 2011100368541A CN 201110036854 A CN201110036854 A CN 201110036854A CN 102130329 A CN102130329 A CN 102130329A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a lithium ion battery film cathode containing a porous polymer elastomer, which comprises the steps of: loading a high-capacity nano particle subjected to surface grafting treatment in a high-conductivity polymer with a directional nano channel by adopting suction filtration, rolling and electrophoresis ways and coating on a current collector copper foil. The lithium ion battery film cathode prepared by adopting the method can greatly inhibit capacity attenuation of the high-capacity nano particle, caused by volume expansion, pulverization and secondary agglomeration, in charge and discharge processes. The film cathode prepared in the invention keeps the advantage of high capacity of the nano particle, and has excellent circulating property. In addition, multiple nano channels in the polymer elastomer can ensure rapid transmission of ions and shorten a transmission path, thereby ensuring excellent multiplying power property of the cathode. The elastic characteristic of the polymer elastomer ensures that volume change of an active substrate in a lithium insertion/extraction process does not influence electric contact property between a coating layer and fluid. The invention is suitable for industrialized production.
Description
Technical field
The invention discloses a kind of elastomeric lithium ion cell film negative pole of porous polymer preparation method that contains, particularly a kind ofly have high power capacity and excellent cycle performance, include porous polymer elastomeric component and high power capacity nano particle contain the elastomeric lithium ion cell film negative pole of porous polymer preparation method.Belong to technical field of electrochemistry.
Background technology
Fields such as electric motor car are more and more urgent to the demand of high-performance lithium ion battery.At present, with the commercialization lithium ion battery of graphite-like raw material of wood-charcoal material, because the low defectives such as (theoretical capacity 372mAh/g) of charcoal class negative pole specific capacity has seriously hindered further developing of capacity of lithium ion battery as negative material.Develop the high power capacity negative material that substitutes the raw material of wood-charcoal material in recent years, as Al, Sn, Ge metal and alloy thereof and nanometer Si and alloy thereof, although the very high lithium of embedding first capacity is arranged, but owing in the doff lithium process big change in volume can take place subsequently, cause the efflorescence of material, thereby secondary agglomeration slowly makes active material lose activity, make that the capacity attenuation of these materials is very fast, in addition, change in volume in the doff lithium process can make also to lose closely between negative plate and the collector and electrically contact that these high-capacity material also do not have the large-scale commercial applications application up till now.Therefore, it is great that research improves the technical meaning of these high power capacity negative materials.
Recently, have high embedding lithium capacity first but take place easily in the doff lithium process and done a large amount of work aspect the chemical property of material of volumetric expansion improving these, nanometer is to improve the effective way of these material cycle performances, yet nanometer can not fundamentally solve expansion, efflorescence causes the defective that the internal resistance of cell increases, cycle performance worsens; Nano thin-film has high specific capacity, excellent cycle performance and high rate charge-discharge performance, but its effective active matter is less, and the preparation condition harshness; Nano wire and nanotube are effective to the expansion that suppresses charge and discharge process, but the polarization of the nano wire under high current density strengthens, thereby have influenced the high rate performance and the cycle life of material.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and a kind of capacity height, good cycle be provided contain the elastomeric lithium ion cell film negative pole of porous polymer preparation method.
A kind of elastomeric lithium ion cell film negative pole of porous polymer preparation method that contains of the present invention comprises the steps:
The first step: preparation includes the suspension that surface modification treatment is crossed the high power capacity nano particle
1.1 the high power capacity nano particle is carried out surface modification
Get granularity 1-100nm, first embedding lithium capacity more than 500mAh/g nanometer Al, Sn, Ge metal and alloy thereof or a kind of high power capacity nano particle in nanometer Si and the alloy thereof place blender to stir, simultaneously, drip surface modifier, obtain the high power capacity nano particle after the surface modification; The speed of described stirring is 500-5000r/min, and the time is 15-120min; The addition of described surface modifier is ten thousand of a high power capacity nano particle quality/to one thousandth, and described surface modifier is selected from a kind of in silane coupler, stearic acid or the titanate coupling agent;
1.2 preparation includes the suspension of surface modification high power capacity nano particle
High power capacity nano particle with surface modification treatment is crossed is distributed in the volatilizable organic solvent by ultrasonic, forms the high power capacity nanoparticle suspension, and solid content is 1-20% in the mixed liquor; Described volatilizable organic solvent is selected from a kind of in toluene, dimethylbenzene, methyl alcohol, ethanol, the acetone; Described ultrasonic dispersion ultrasonic intensity is 20-1000kHz, and the time is 15-120min;
Second step: the preparation of face coat
From the orienting stephanoporate conducting polymer elastomer of porous polythiophene, porous polypyrrole or porous polyaniline, choose a kind of, and be placed in the funnel that is provided with core, then the high power capacity nanoparticle suspension of first step gained is added in the funnel, carry out suction filtration simultaneously; Realize that the high power capacity nanoparticle-loaded is in the hole of orienting stephanoporate polymer elastomer; Or
The high power capacity nanoparticle suspension of first step gained is added drop-wise to orienting stephanoporate polymer elasticity surface, uses the pair roller roll extrusion then; Realize that the high power capacity nanoparticle-loaded is in the hole of orienting stephanoporate polymer elastomer; Obtain the high power capacity nano particle and be compounded in face coat in the orienting stephanoporate polymer elastomer;
The 3rd step was coated in second face coat that goes on foot gained on the Copper Foil by mechanical coating method, in 30-80 ℃ of oven dry, promptly got film cathode of the present invention, and the thickness of described face coat is 10-150um.
A kind of another kind of preparation method of the elastomeric lithium ion cell film negative pole of porous polymer that contains of the present invention comprises the steps:
The first step: get a kind of in the orienting stephanoporate polymer elastomer of porous polythiophene, porous polypyrrole or the porous polyaniline of 1-100nm of aperture; Described orienting stephanoporate polymer elastomer is coated on the Copper Foil collector by mechanical coating method, and coating thickness is 10-150um;
Second the step: get granularity 1-100nm, first embedding lithium capacity more than 500mAh/g nanometer Al, Sn, Ge metal and alloy thereof or a kind of high power capacity nano particle in nanometer Si and the alloy thereof place blender to stir, simultaneously, drip surface modifier, obtain the high power capacity nano particle after the surface modification; The speed of described stirring is 500-5000r/min, and the time is 15-120min; The addition of described surface modifier is ten thousand of a high power capacity nano particle quality/to one thousandth, and described surface modifier is selected from a kind of in silane coupler, stearic acid or the titanate coupling agent;
Then with the high power capacity nano particle wiring solution-forming after solvent, conduction inorganic salts and the surface modification, described conduction inorganic salts account for the 0.2-0.8% of described solution quality, high power capacity nano particle after the described surface modification accounts for the 0.02-5% of described solution quality, described solvent is selected from a kind of in isopropyl alcohol, the acetone or alcohol, and described conduction inorganic salts are selected from a kind of in magnesium nitrate, anhydrous magnesium chloride, aluminium chloride or the aluminum nitrate;
The 3rd step, the coating that the first step is obtained the copper collector of polymer as cathode plate, platinized platinum or high solid graphite sheet as plate, place resulting solution of second step under the state that constantly stirs negative electrode, plate, implement electrophoresis, promptly obtain film cathode of the present invention; Pole span is 1-50cm between the described yin, yang pole plate, and voltage is 2-5V between the two poles of the earth, electrophoresis time 1-60min.
The present invention is owing to adopt above-mentioned process, and prepared negative pole is made of Copper Foil collector, porous polymer elastomer and high power capacity nano active material.Prepared material has the advantage of nano active material high power capacity; In addition, because porous elastomers has wherein carried out the nano active particle effectively separately, avoided like this owing to active material with lithium alloyage/removal alloying process in volumetric expansion, efflorescence secondary agglomeration appears, also just avoided because the capacity attenuation that secondary agglomeration causes; The elastic characteristic of polymer-coated layer on the copper collector can not make electrically contacting between coat and the copper collector degenerate owing to the change in volume in the active material doff lithium process; Moreover the Donna rice grain pattern road feature in the elastomer can guarantee the quick of ion transfer and shorten delivering path, thereby can make that the high rate performance of this negative pole is good.
The prepared material of the present invention has the following advantages:
1, negative pole that the present invention obtains need not compressing tablet, film forming, and the product that obtains can be directly used in the battery assembling;
2, in the prepared film of the present invention, include the nano particle of high power capacity, thereby this invention can obtain the film cathode of high power capacity;
3, in the prepared film of the present invention, porous elastomers has carried out the nano active particle effectively separately, avoided like this owing to secondary agglomeration appears in active material volumetric expansion in lithium alloyage/removal alloying process, efflorescence, also just avoided because the capacity attenuation that secondary agglomeration causes; The elastic characteristic of coat on the copper collector can not make electrically contacting between coat and the copper collector degenerate owing to the change in volume in the active material doff lithium process; Moreover the Donna rice grain pattern road feature of elastomer heavy can guarantee the quick of ion transfer and shorten delivering path, thereby can make that the high rate performance of this negative pole is good.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not so limited.
Embodiment 1 is a raw material with commercial nanometer Si and commodity porous, electrically conductive polypyrrole (PPy) elastomer, prepares film cathode by the mechanical stitch method
The first step adds silane coupler several times and makes the nano-silicon that surface grafting is handled among the nanometer Si of high-speed stirred; The particle of nanometer Si is 20-30nm, and the silane coupler addition is 5/10000ths of a nanometer Si granular mass, and institute's employing stirring speed is 2000r/min, and mixing time is 60min;
In second step, the high power capacity nano particle that the surface modification treatment that previous step is obtained is crossed is distributed in the ethanol by ultrasonic, and containing admittedly in the mixed liquor is 5%; Described ultrasonic dispersion ultrasonic intensity is 800kHz, and the time is 30min.
The 3rd the step, select for use tensile strength 20-30MPa, conductance 180S/cm, hole size be 30-40nm, pore volume content at 60-70%, thickness is the commodity porous PP y of 15um.At first PPy is used the scraper blade coating to the special-purpose Copper Foil of lithium ion battery, and its weight of weighing; Then, the alcohol mixeding liquid that will include nano particle by the mode that drips is added drop-wise to the PPy surface, by the pair roller roll extrusion repeatedly; Constantly repeat dropping-roll extrusion process, the pole piece that obtains at last brushes away with the Si powder of hairbrush with the surface, calculates the content of nanometer Si in the pole piece, just obtains the pole piece of different Si content; With the conduct of Li sheet electrode is carried out electro-chemical test at last.Nanometer Si content in the used pole piece of present embodiment for the deduction Copper Foil after the pole piece gross mass 50%.
The test of pole piece battery performance: gained pole piece and metal lithium sheet are formed the electrochemistry embedding of half-cell test material/take off the lithium performance, and electrolyte is commercially available 1M LiPF6/EC+DMC solution.Utilize the Land battery test system that above-mentioned half-cell is at room temperature carried out the constant current charge-discharge performance test, charge-discharge magnification is 1200mA/g and 8400mA/g, and the charging/discharging voltage scope is 0-3V.
The battery performance testing result: 1. 840mA/g rate charge-discharge testing result shows, the cycle efficieny first of present embodiment material is near 90%, first reversible capacity 1890mAh/g; And present business-like CMS is at the about 305mAh/g of reversible capacity first of 74.4mA/g rate charge-discharge.In preceding 100 circulations, the capacity attenuation of each circulation of present embodiment is less than 0.1%, and promptly 100 circulation back capability retentions are higher than 91% (promptly the capacity after 100 circulations is 1720mAh/g); But commercial CMS is 84% at the capability retention after 100 circulations (promptly the capacity after 100 circulations is 256mAh/g).2. 8400mA/g rate charge-discharge testing result shows, 500 circulation back capacity of present embodiment material are higher than 1000mAh/g; And the capacity of present business-like CMS under high magnification so, after 500 circulations is less than 80mAh/g.Test result shows that the present embodiment material has high capacity and outstanding cycle performance of battery, especially has the cycle characteristics under the big multiplying power.
Embodiment 2 is a raw material with commercial nanometer Sn-Co alloyed powder and commodity porous, electrically conductive polythiophene (PTh) elastomer, prepares film cathode by the electrochemistry electrophoresis method
Select for use tensile strength 20-30MPa, conductance 150S/cm, hole size be 40-50nm, pore volume content at 60-70%, thickness is the commodity porous PTh of 15um, and to select granularity for use be that the nanometer Sn-Co powder of 20-30nm is a raw material.
The first step uses the scraper blade coating to the special-purpose Copper Foil of lithium ion battery selected PTh, and its weight of weighing.
In second step, preparation comprises the electrophoresis liquid of high power capacity nanometer Sn-Co particle.At first, titanate coupling agent is added several times make the nano-silicon that surface grafting is handled among the nanometer Sn-Co of high-speed stirred; The particle diameter of nanometer Sn-Co particle is 20-30nm, and the titanate coupling agent addition is 5/10000ths of a nanometer Sn-Co granular mass, and institute's employing stirring speed is 2000r/min, and mixing time is 60min; Then, the nano particle wiring solution-forming after solvent, conduction inorganic salts and the grafting processing, the conduction inorganic salts account for 0.8% of electrophoresis liquid quality, and the nano particle after grafting is handled accounts for 2% of electrophoresis liquid quality, wherein solvent is an isopropyl alcohol, and the conduction inorganic salts refer to anhydrous magnesium chloride.
The 3rd step, carry out the electrophoresis operation, make the nano particle electrophoresis enter the nanochannel of polymer.The coating that the first step is obtained the copper collector of polymer as negative electrode, as plate, place platinized platinum or high solid graphite sheet continuous stirring electrophoresis liquid to implement electrophoresis on the anode and cathode pole plate, pole span is 1.5cm between the cathode-anode plate, voltage is 5V between the two-stage, electrophoresis time 20min.
Obtain the film cathode of Sn-Co content 70% in the polymer film at last.
The test of pole piece battery performance: gained pole piece and metal lithium sheet are formed the electrochemistry embedding of half-cell test material/take off the lithium performance, and electrolyte is commercially available 1M LiPF6/EC+DMC solution.Utilize the Land battery test system that above-mentioned half-cell is at room temperature carried out the constant current charge-discharge performance test, charge-discharge magnification is 100mA/g and 300mA/g, and the charging/discharging voltage scope is 0-1.5V.
The battery performance testing result: 1. 100mA/g rate charge-discharge testing result shows, the cycle efficieny first of present embodiment material is near 90%, first reversible capacity 552mAh/g; And present business-like CMS is at the about 305mAh/g of reversible capacity first of 74.4mA/g rate charge-discharge.After 100 circulations, the present embodiment capacity is 495mAh/g; But commercial CMS is 84% at the capability retention after 100 circulations (promptly the capacity after 100 circulations is 256mAh/g).2. 300mA/g rate charge-discharge testing result shows, 100 circulation back capacity of present embodiment material are higher than 380mAh/g; And the capacity of present business-like CMS under high magnification so, after 100 circulations is less than 80mAh/g.Test result shows that the present embodiment material has high capacity and outstanding cycle performance of battery, especially has the cycle characteristics under the big multiplying power.
Embodiment 3 is a raw material with commercial nanometer Sn and commodity porous, electrically conductive polyaniline (PAn) elastomer, prepares film cathode by suction filtration
The first step, the surface treatment of nanometer Sn and dispersion.
At first, nanometer Sn is carried out surface treatment.The nanometer Sn particle of getting 20-30nm places blender to stir, and simultaneously, drips surface modifier, obtains the high power capacity nano particle after the surface modification; Present embodiment institute employing stirring speed is 1000r/min, and mixing time is 60min; The surface modifier that is adopted is a stearic acid, and its addition is 3/10000ths of a nanometer Sn mass particle.
Secondly, be distributed in the volatilizable acetone soln surface-treated nanometer Sn is ultrasonic, form the high power capacity nanoparticle suspension, it is 10% that the consolidating of this suspension contains; Described ultrasonic dispersion ultrasonic intensity is 1000kHz, and the time is 45min.
Second step, the preparation of face coat.
Select for use tensile strength 20-30MPa, conductance 180S/cm, hole size be 30-40nm, pore volume content at 60-70%, thickness is the commodity porous, electrically conductive polyaniline (PAn) of 25um, as the supporting body of high power capacity Sn.PAn places the funnel that is provided with core with this porous, then the high power capacity nanoparticle suspension of first step gained is added in the funnel, carries out suction filtration simultaneously; Thereby made the porous Sn-PAn coating of present embodiment.
The 3rd step was coated to the second step coating that obtains on the copper collector, then 80 ℃ of vacuumizes, promptly obtained the film cathode of present embodiment.Sn content is 80% (mass percent) in the polymers obtained rete.
Electro-chemical test is with embodiment 2.
The battery performance testing result: 1. 100mA/g rate charge-discharge testing result shows, the cycle efficieny first of present embodiment material is near 88%, first reversible capacity 561mAh/g; And present business-like CMS is at the about 305mAh/g of reversible capacity first of 74.4mA/g rate charge-discharge.After 100 circulations, the present embodiment capacity is 505mAh/g; But commercial CMS is 84% at the capability retention after 100 circulations (promptly the capacity after 100 circulations is 256mAh/g).2. 300mA/g rate charge-discharge testing result shows, 100 circulation back capacity of present embodiment material are higher than 405mAh/g; And the capacity of present business-like CMS under high magnification so, after 100 circulations is less than 80mAh/g.Test result shows that the present embodiment material has high capacity and outstanding cycle performance of battery, especially has the cycle characteristics under the big multiplying power.
Claims (8)
1. one kind contains the elastomeric lithium ion cell film negative pole of porous polymer preparation method, comprises the steps:
The first step: preparation includes the suspension that surface modification treatment is crossed the high power capacity nano particle
1.1 the high power capacity nano particle is carried out surface modification
Get granularity 1-100nm, first embedding lithium capacity more than 500mAh/g nanometer Al, Sn, Ge metal and alloy thereof or a kind of high power capacity nano particle in nanometer Si and the alloy thereof place blender to stir, simultaneously, drip surface modifier, obtain the high power capacity nano particle after the surface modification;
1.2 preparation includes the suspension of surface modification high power capacity nano particle
High power capacity nano particle with surface modification treatment is crossed is distributed in the volatilizable organic solvent by ultrasonic, forms the high power capacity nanoparticle suspension, and solid content is 1-20% in the mixed liquor;
Second step: the preparation of face coat
From the orienting stephanoporate conducting polymer elastomer of porous polythiophene, porous polypyrrole or porous polyaniline, choose a kind of, and be placed in the funnel that is provided with core, then the high power capacity nanoparticle suspension of first step gained is added in the funnel, carry out suction filtration simultaneously; Realize that the high power capacity nanoparticle-loaded is in the hole of orienting stephanoporate polymer elastomer; Or
The high power capacity nanoparticle suspension of first step gained is added drop-wise to orienting stephanoporate polymer elasticity surface, uses the pair roller roll extrusion then; Realize that the high power capacity nanoparticle-loaded is in the hole of orienting stephanoporate polymer elastomer;
Obtain the high power capacity nano particle and be compounded in face coat in the orienting stephanoporate polymer elastomer;
The 3rd step was coated in second face coat that goes on foot gained on the Copper Foil by mechanical coating method, and the thickness of described face coat is 10-150um, in 30-80 ℃ of oven dry, promptly gets a kind of elastomeric lithium ion cell film negative pole of porous polymer that contains.
2. one kind contains the elastomeric lithium ion cell film negative pole of porous polymer preparation method, comprises the steps:
The first step: get a kind of in the orienting stephanoporate polymer elastomer of porous polythiophene, porous polypyrrole or the porous polyaniline of 1-100nm of aperture; Described orienting stephanoporate polymer elastomer is coated on the Copper Foil collector by mechanical coating method, and coating thickness is 10-150um;
Second the step: get granularity 1-100nm, first embedding lithium capacity more than 500mAh/g nanometer Al, Sn, Ge metal and alloy thereof or a kind of high power capacity nano particle in nanometer Si and the alloy thereof place blender to stir, simultaneously, drip surface modifier, obtain the high power capacity nano particle after the surface modification;
Then with the high power capacity nano particle wiring solution-forming after solvent, conduction inorganic salts and the surface modification;
The 3rd step, the coating that the first step is obtained the copper collector of polymer as cathode plate, platinized platinum or high solid graphite sheet as plate, place resulting solution of second step under the state that constantly stirs negative electrode, plate, implement electrophoresis, promptly obtain a kind of elastomeric lithium ion cell film negative pole of porous polymer that contains.
3. a kind of preparation method who contains the elastomeric lithium ion cell film negative pole of porous polymer according to claim 1 and 2 is characterized in that: the mixing speed of described blender is 500-5000r/min, and the time is 15-120min.
4. a kind of preparation method who contains the elastomeric lithium ion cell film negative pole of porous polymer according to claim 1 and 2, it is characterized in that: the addition of described surface modifier is ten thousand of a high power capacity nano particle quality/to one thousandth, and described surface modifier is selected from a kind of in silane coupler, stearic acid or the titanate coupling agent.
5. a kind of preparation method who contains the elastomeric lithium ion cell film negative pole of porous polymer according to claim 1 and 2 is characterized in that: described volatilizable organic solvent is selected from a kind of in toluene, dimethylbenzene, methyl alcohol, ethanol, the acetone.
6. a kind of preparation method who contains the elastomeric lithium ion cell film negative pole of porous polymer according to claim 1 and 2 is characterized in that: described ultrasonic dispersion ultrasonic intensity is 20-1000kHz, and the time is 15-120min.
7. a kind of preparation method who contains the elastomeric lithium ion cell film negative pole of porous polymer according to claim 2, it is characterized in that: described conduction inorganic salts account for the 0.2-0.8% of described solution quality, high power capacity nano particle after the described surface modification accounts for the 0.02-5% of described solution quality, described solvent is selected from a kind of in isopropyl alcohol, the acetone or alcohol, and described conduction inorganic salts are selected from a kind of in magnesium nitrate, anhydrous magnesium chloride, aluminium chloride or the aluminum nitrate.
8. a kind of preparation method who contains the elastomeric lithium ion cell film negative pole of porous polymer according to claim 2 is characterized in that: pole span is 1-50cm between the described yin, yang pole plate, and voltage is 2-5V between the two poles of the earth, electrophoresis time 1-60min.
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Cited By (6)
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CN102303007A (en) * | 2011-09-02 | 2012-01-04 | 深圳市格瑞普电池有限公司 | Method for coating electrode plate for lithium ion battery, electrode plate for lithium ion battery, and lithium ion battery |
CN103050192A (en) * | 2012-12-20 | 2013-04-17 | 中国科学技术大学 | Elastic conductor based on silver nanowire as well as preparation method and application thereof |
CN103106950A (en) * | 2013-01-10 | 2013-05-15 | 中国航空工业集团公司北京航空材料研究院 | Conductive foam and preparation method thereof |
CN103996834A (en) * | 2014-06-14 | 2014-08-20 | 哈尔滨工业大学 | Silicon-base negative material with silane coupling agent and conductive polymer two-layer cladding structure as well as preparation method and application of material |
CN108123104A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of three continuous Si/C porous electrodes and its application |
CN109768263A (en) * | 2019-03-01 | 2019-05-17 | 江苏赛清科技有限公司 | A kind of lithium battery high capacity composite negative pole material and preparation method thereof |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102303007A (en) * | 2011-09-02 | 2012-01-04 | 深圳市格瑞普电池有限公司 | Method for coating electrode plate for lithium ion battery, electrode plate for lithium ion battery, and lithium ion battery |
CN103050192A (en) * | 2012-12-20 | 2013-04-17 | 中国科学技术大学 | Elastic conductor based on silver nanowire as well as preparation method and application thereof |
CN103050192B (en) * | 2012-12-20 | 2015-08-12 | 中国科学技术大学 | A kind of elastic conductor based on nano silver wire and its preparation method and application |
CN103106950A (en) * | 2013-01-10 | 2013-05-15 | 中国航空工业集团公司北京航空材料研究院 | Conductive foam and preparation method thereof |
CN103996834A (en) * | 2014-06-14 | 2014-08-20 | 哈尔滨工业大学 | Silicon-base negative material with silane coupling agent and conductive polymer two-layer cladding structure as well as preparation method and application of material |
CN103996834B (en) * | 2014-06-14 | 2016-08-24 | 哈尔滨工业大学 | A kind of silicon based anode material with silane coupler and conducting polymer double-coating structure and preparation method and application |
CN108123104A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of three continuous Si/C porous electrodes and its application |
CN109768263A (en) * | 2019-03-01 | 2019-05-17 | 江苏赛清科技有限公司 | A kind of lithium battery high capacity composite negative pole material and preparation method thereof |
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Application publication date: 20110720 |