CN104009213A - Manufacturing method and application of amino functional silicon-based negative electrode materials - Google Patents
Manufacturing method and application of amino functional silicon-based negative electrode materials Download PDFInfo
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Abstract
The invention discloses a manufacturing method and application of amino functional silicon-based negative electrode materials. The method comprises the steps of (1) preparing chemical copper plating solutions, (2) performing electroless copper plating on the surface of elemental silicon powder, and (3) performing in-situ polymerization on phenylamine on the surface of the copper plating layer. The amino functional silicon-based negative electrode materials manufactured through the method are doped in negative electrode materials, in graphite, capable of being used for manufacturing a lithium ion battery. A metal copper layer is plated on the silica powder surface through the electroless plating method, due to the fact that nitrogen atoms in aniline monomer molecules are provided with lone pair electrons, the aniline monomer molecules can be cooperated with a hollow track of a dth layer of the outer sides of the metal copper atoms, active sites are formed, in-situ polymerization is performed on aniline monomers on the surface of copper, polyaniline is formed, and therefore amino on the silicon powder surface can be functionalized. Expansion and pulverization phenomena of the silicon-based negative electrode materials in the circulation are improved, the silicon-based negative electrode materials have the higher first-time coulombic efficiency and the better circulation stability, and the circulating performance of the silicon-based negative electrode materials is further improved.
Description
Technical field
The invention belongs to lithium ion battery negative material and material surface modifying technology field, relate to a kind of preparation method and application of functional amido silicon based anode material.
Background technology
In the last few years, lithium ion battery had the little and advantages of environment protection of high-energy-density, high output voltage, low self-discharge, memory effect with respect to secondary cells such as traditional lead-acid battery, iron cell, Ni-MH batteries, and was widely used and studies.The performance of lithium ion battery critical material is the important deciding factor of battery performance, and it is global scientific research focus that the exploitation of negative material improves.The negative materials such as silicon materials, material with carbon element, tin material, lithium titanate, metal oxide are studied widely.But there is the defects such as cycle performance is poor, specific energy density is low, cost is high, poor stability, consistency problem in the lithium-ion battery system of these negative material assemblings, is difficult to meet the requirement of power energy-storage battery.
silicon based anode material, because its theoretical specific capacity exceedes 4200 mAh/g, embedding lithium current potential is low, actual specific capacity is greater than 3000 mAh/g, in advantages such as natural rich content, cost of material are relatively cheap, is the study hotspot of lithium ion battery negative material always.The shortcoming severe inhibition such as but coulomb efficiency first of silicon materials is low, high rate performance is poor, cycle performance is poor the large-scale application of silicon based anode material in lithium ion battery.
For the silicon based anode material of development cycle excellent performance, researcher has developed multiple technologies means silicon materials has been carried out to modification raising.Graphite, hard carbon, pitch, carbon nano-tube, carbon nano-fiber, metal nano-tube etc. have been used to coated silicon based anode material.
CN1865500A, the denomination of invention method of electroless copper " a kind of on silicon chip " disclose a kind of preparation method of copper modified silicon material.The method is containing in the hydrofluoric acid solution of mantoquita, introduces copper crystal seed as catalyst, and then carry out copper facing at silicon chip surface.There is the shortcoming such as operational hazards, reaction time length in the method.
CN101612554A, denomination of invention " preparation method of conducting polymer modified active carbon " disclose a kind of method of utilizing aminated compounds controlledly synthesis functional amido carbon negative pole material.The method utilizes conventional method to make aniline monomer carry out home position polymerization reaction at activated carbon surface, obtains active carbon/conducting polymer composite material.But the method exists complex steps, reaction to be difficult to the shortcomings such as control, and too high cost has hindered its business-like process.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application of functional amido silicon based anode material, the method is simple, environmental protection, and process stabilizing is reliable, and favorable reproducibility is applicable to suitability for industrialized production.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for functional amido silicon based anode material, its step is as follows:
(1) preparation of chemical bronze plating liquid
Silica flour is added in copper sulfate solution to ultrasonic dispersion treatment; Wherein: the preparation method of silica flour is the one of vapor phase method, sol-gel processing, the precipitation method, microemulsion method, ball-milling method; The particle size interval scope of silica flour is between 20 to 8000nm, and copper sulfate solution concentration is 1.5-15g/L, and ultrasonic power is 1.5-2w/cm, and supersonic frequency is 20-30kHz, and ultrasonic time is 0.5-1h, and the mass ratio of copper sulphate and silica flour is 0.75:1-7.5:1;
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under protective atmosphere, drips sodium borohydride aqueous solution to reacting complete, washing, suction filtration, vacuumize; Wherein: sodium borohydride aqueous solution concentration is 0.9-9g/L, the addition of sodium borohydride aqueous solution is identical with the addition of copper sulfate solution, time for adding is 1-5min, reaction time is 5-10min, vacuumize temperature is 45-55 DEG C, the vacuumize time is 10-12 h, and the mass ratio of copper coating and silica flour is 1:40-1:3;
(3) aniline is at copper coating in situ Polymerization
Aniline monomer and copper modification silica flour are carried out to ultrasonic blend in the acid solution system of Bronsted acid, then add ammonium persulfate, carry out in-situ polymerization, use the alternately rear suction filtration of washing, the vacuumize of distilled water and ethanol, obtain functional amido silicon based anode material; Wherein: Bronsted acid is one or more the mixture in hydrochloric acid, DBSA, camphorsulfonic acid, p-methyl benzenesulfonic acid, pyrovinic acid, normal-butyl/ethyl phosphonic acid, n-decane base phosphoric acid, benzyl phosphoric acid, benzoic acid, the mass ratio of ammonium persulfate and aniline is 1:2-1:4, polymeric reaction temperature is 0-10 DEG C, polymerization reaction time is 4-10 h, vacuumize temperature is 50-60 DEG C, the vacuumize time is 10-12 h, and the mass ratio of copper modification silica flour and aniline is 4:1-1:1.
Functional amido silicon based anode material prepared by said method is entrained in the negative material that can be used for preparing lithium ion battery in graphite, and wherein functional amido silicon based anode material accounts for 1 ~ 98% of content of graphite.
The present invention plates layer of metal copper by the method for chemical plating at silicon powder surface, because the nitrogen-atoms in aniline monomer molecule has lone pair electrons, can with the unoccupied orbital generation coordination of the outer d layer of metallic copper atom, form avtive spot, then make aniline monomer at copper in situ Polymerization, form polyaniline, therefore can make silicon powder surface functional amido, and then improve the expansion of silicon based anode material in circulation, powder phenomenon-tion, make silicon based anode material there is higher coulomb efficiency first and good cyclical stability, further improve the cycle performance of silicon based anode material.
Advantage of the present invention is as follows:
(1) the functional amido silicon based anode material that prepared by the present invention has higher specific capacity with respect to the silicon-based anode of prior art, particularly the cycle performance of existing silicium cathode is carried out significantly improving, after being entrained in graphite, the performance of graphite cathode material is had significantly and promoted.
(2) the present invention has significantly improved coulomb efficiency and the cyclical stability first of silicon based anode material, and process stabilizing is reliable.
(3) preparation method of functional amido silicon based anode material of the present invention carries out under room temperature condition, and evenly, simple to operate, process stabilizing is reliable in reaction, and favorable reproducibility is applicable to extend to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the SEM figure of (comparative example) before silicon powder surface copper facing;
Fig. 2 is the SEM figure after silicon powder surface copper facing;
Fig. 3 is the assembling schematic diagram of amino-functionalization silicon based anode material;
Fig. 4 is the functional amido silicon based anode material of each embodiment and the electrochemistry cycle performance of comparative example diagram;
Fig. 5 is the charging and discharging curve of functional amido silicon based anode material in embodiment 4.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described; but do not limit to so; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
embodiment 1:
The present embodiment provides a kind of preparation method of functional amido silicon based anode material, and implementation step is as follows:
(1) preparation of chemical bronze plating liquid
0.2g nano silica fume is added in the copper sulfate solution of 100 mL 0.75 g/L, ultrasonic dispersion treatment 0.5 h, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz.
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under nitrogen protection, drip 100ml 0.45g/L sodium borohydride aqueous solution to reacting complete, time for adding is 1min, reaction time is 5min, washing, suction filtration, vacuumize, and vacuumize temperature is 55 DEG C, the vacuumize time is 10 h, and the mass ratio of copper coating and silica flour is about 1:20;
(3) aniline is at copper coating in situ Polymerization
Ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.045 g aniline monomer and 0.2g copper modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 DEG C, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0216g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 10 h, after reaction finishes, use distilled water and ethanol alternately to wash 2-3 time, use circulating water pump suction filtration final vacuum dry, vacuumize temperature is 60 DEG C, the vacuumize time is 12 h, obtain functional amido silicon based anode material.The mass ratio of copper modification silica flour and aniline is about 4:1.
Fig. 3 is the assembling schematic diagram of amino-functionalization silicon based anode material, as shown in Figure 3, outside the copper coating of silicon powder surface, original position synthesized polyaniline.
From electrochemistry cycle performance in Fig. 4, functional amido silicon based anode material has good cycle performance, initial charge capacity 2301.78 mAh/g of material, first charge-discharge efficiency is 69.8%, after 200 circulations, charging capacity is 1388.14 mAh/g, Capacitance reserve, more than 1380 mAh/g, has excellent performance.
embodiment 2:
The present embodiment provides a kind of preparation method of functional amido silicon based anode material, and implementation step is as follows:
(1) preparation of chemical bronze plating liquid
0.2g nano silica fume is added in the copper sulfate solution of 100 mL 1.5 g/L, ultrasonic dispersion treatment 0.5 h, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz.
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under nitrogen protection, drip 100mL 0.9 g/L sodium borohydride aqueous solution to reacting complete, time for adding is 1min, reaction time is 5min, washing, suction filtration, vacuumize, and vacuumize temperature is 55 DEG C, the vacuumize time is 10 h, and the mass ratio of copper coating and silica flour is about 1:10;
(3) aniline is at copper coating in situ Polymerization
Ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.045 g aniline monomer and 0.2g copper modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 DEG C, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0216g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 4-10 h, after reaction finishes, use distilled water and ethanol alternately to wash 2-3 time, use circulating water pump suction filtration final vacuum dry, vacuumize temperature is 60 DEG C, the vacuumize time is 12 h, obtain functional amido silicon based anode material.The mass ratio of copper modification silica flour and aniline is about 4:1.
As seen from Figure 2, for the comparative example in Fig. 1, the particle outer cladding after reunion the nano level copper layer of one deck.After this explanation electroless copper, the particle shape after agglomerated " solidifies ", and this can be to silicon volumetric expansion, alleviate from collector this problem that comes off.
From electrochemistry cycle performance in Fig. 4, functional amido silicon based anode material has good cycle performance, initial charge capacity 2163.76 mAh/g of material, first charge-discharge efficiency is 67.3%, after 200 circulations, charging capacity is 1601.80 mAh/g, Capacitance reserve, in 1600 mAh/g left and right, has excellent performance.
embodiment 3:
The present embodiment provides a kind of preparation method of functional amido silicon based anode material, and implementation step is as follows:
(1) preparation of chemical bronze plating liquid
0.2g nano silica fume is added in the copper sulfate solution of 100 mL 0.75 g/L, ultrasonic dispersion treatment 0.5 h, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz.
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under nitrogen protection, drip 100ml 0.45g/L sodium borohydride aqueous solution to reacting complete, time for adding is 1min, reaction time is 5min, washing, suction filtration, vacuumize, and vacuumize temperature is 55 DEG C, the vacuumize time is 10 h, and the mass ratio of copper coating and silica flour is about 1:20;
(3) aniline is at copper coating in situ Polymerization
Ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.06 g aniline monomer and 0.2g copper modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 DEG C, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0288g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 4-10 h, after reaction finishes, use distilled water and ethanol alternately to wash 2-3 time, use circulating water pump suction filtration final vacuum dry, vacuumize temperature is 60 DEG C, the vacuumize time is 12 h, obtain functional amido silicon based anode material.The mass ratio of copper modification silica flour and aniline is about 3:1.
From electrochemistry cycle performance in Fig. 4, functional amido silicon based anode material has good cycle performance, initial charge capacity 1376.78 mAh/g of material, first charge-discharge efficiency is 69%, after 200 circulations, charging capacity is 1294.54 mAh/g, Capacitance reserve, more than 1290 mAh/g, has excellent performance.
embodiment 4:
The present embodiment provides a kind of preparation method of functional amido silicon based anode material, and implementation step is as follows:
(1) preparation of chemical bronze plating liquid
0.2g nano silica fume is added in the copper sulfate solution of 100 mL 1.5 g/L, ultrasonic dispersion treatment 0.5 h, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz.
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under nitrogen protection, drip 100ml 0.9g/L sodium borohydride aqueous solution to reacting complete, time for adding is 1min, reaction time is 5min, washing, suction filtration, vacuumize, and vacuumize temperature is 55 DEG C, the vacuumize time is 10 h, and the mass ratio of copper coating and silica flour is about 1:10;
(3) aniline is at copper coating in situ Polymerization
Ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.06 g aniline monomer and 0.2g copper modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 DEG C, drip dodecylbenzenesulfonic acid solution 30 mL of 3.1% percentage by volume that contains 0.0288g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 4-10 h, after reaction finishes, use distilled water and ethanol alternately to wash 2-3 time, use circulating water pump suction filtration final vacuum dry, vacuumize temperature is 60 DEG C, the vacuumize time is 12 h, obtain functional amido silicon based anode material.The mass ratio of copper modification silica flour and aniline is about 3:1.
From electrochemistry cycle performance in Fig. 4, functional amido silicon based anode material has good cycle performance, initial charge capacity 1115 mAh/g of material, first charge-discharge efficiency is 67%, after 200 circulations, charging capacity is 977.34 mAh/g, Capacitance reserve, in 980 mAh/g left and right, has excellent performance.
From first three charging and discharging curve in Fig. 5, the functional amido silicon based anode material in embodiment has higher efficiency first (67%).
embodiment 5:
The present embodiment provides a kind of functional amido silicon based anode material preparation method and application, and implementation step is as follows:
(1) preparation of chemical bronze plating liquid
0.2g nano silica fume is added in the copper sulfate solution of 100 mL 1.5 g/L, ultrasonic dispersion treatment 0.5 h, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz.
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under nitrogen protection, drip 100ml 0.9g/L sodium borohydride aqueous solution to reacting complete, time for adding is 1min, reaction time is 5min, washing, suction filtration, vacuumize, and vacuumize temperature is 55 DEG C, the vacuumize time is 10 h, and the mass ratio of copper coating and silica flour is about 1:10;
(3) aniline is at copper coating in situ Polymerization
Ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.06 g aniline monomer and 0.2g copper modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 DEG C, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0288g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 4-10 h, after reaction finishes, use distilled water and ethanol alternately to wash 2-3 time, use circulating water pump suction filtration final vacuum dry, vacuumize temperature is 60 DEG C, the vacuumize time is 12 h, obtain functional amido silicon based anode material.The mass ratio of copper modification silica flour and aniline is 3:1.
(4) the functional amido silicon based anode material making in step (3) is mixed with 20% additional proportion and graphite, obtain thering is high power capacity, the negative material for lithium ion battery of good circulation performance.
From electrochemistry cycle performance in Fig. 4, after functional amido silicon based anode material joins in graphite with 20% mass fraction, this composite material has good cycle performance, the initial charge capacity 730.352mAh/g of material, first charge-discharge efficiency is 86%, after 200 circulations, charging capacity is 663.26 mAh/g, and Capacitance reserve, in 660 mAh/g left and right, has excellent performance.
embodiment 6:
The present embodiment provides a kind of functional amido silicon based anode material preparation method and application, and implementation step is as follows:
(1) preparation of chemical bronze plating liquid
0.2g nano silica fume is added in the copper sulfate solution of 100 mL 1.5 g/L, ultrasonic dispersion treatment 0.5 h, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz.
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under nitrogen protection, drip 100ml 0.9g/L sodium borohydride aqueous solution to reacting complete, time for adding is 1min, reaction time is 5min, washing, suction filtration, vacuumize, and vacuumize temperature is 55 DEG C, the vacuumize time is 10 h, and the mass ratio of copper coating and silica flour is about 1:10;
(3) aniline is at copper coating in situ Polymerization
Ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.06 g aniline monomer and 0.2g copper modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 DEG C, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0288g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 4-10 h, after reaction finishes, use distilled water and ethanol alternately to wash 2-3 time, use circulating water pump suction filtration final vacuum dry, vacuumize temperature is 60 DEG C, the vacuumize time is 12 h, obtain functional amido silicon based anode material.The mass ratio of copper modification silica flour and aniline is 3:1.
(4) the functional amido silicon based anode material making in step (3) is mixed with 50% additional proportion and graphite.
From electrochemistry cycle performance in Fig. 4, after functional amido silicon based anode material joins in graphite with 50% ratio, this composite material has good cycle performance, initial charge capacity 1267.88 mAh/g of material, first charge-discharge efficiency is 75.1%, after 200 circulations, charging capacity is 1037.46 mAh/g, and Capacitance reserve, more than 1030 mAh/g, has excellent performance.
Comparative example is undressed elemental silicon, from the electrochemistry cycle performance of alloying silicon based anode material in Fig. 5, the initial charge capacity of material is 3014.79 mAh/g, after 200 circulations, charging capacity is 0.71 mAh/g, first charge-discharge efficiency is 64.8%, and the capability retention of comparative example is very undesirable.
Table 1 is each embodiment material cycle performance contrast.
Table 1
| Electrode material | Embedding lithium capacity (mAh/g) first | Embedding lithium capacity (mAh/g) after 200 times | Coulomb efficiency (%) first |
| Embodiment 1 | 2301.78 | 1388.14 | 69.8 |
| Embodiment 2 | ?2163.76 | 1601.80 | 67.3 |
| Embodiment 3 | 1376.78 | 1294.54 | 69.1 |
| Embodiment 4 | 1115.01 | 977.34 | 67.2 |
| Embodiment 5 | 730.352 | 663.26 | 86.0 |
| Embodiment 6 | 1267.88 | 1037.46 | 75.1 |
| Comparative example | 3014.79 | 0.71 | 64.8 |
Claims (10)
1. a preparation method for functional amido silicon based anode material, is characterized in that described method step is as follows:
(1) preparation of chemical bronze plating liquid
Silica flour is added in copper sulfate solution, ultrasonic dispersion treatment, the mass ratio of controlling copper sulphate and silica flour is 0.75:1-7.5:1;
(2) carry out electroless copper on the surface of simple substance silica flour
Above-mentioned mixed solution is transferred in there-necked flask, under protective atmosphere, drips sodium borohydride aqueous solution to reacting complete, washing, suction filtration, vacuumize, obtain copper modification silica flour, and the mass ratio of copper coating and silica flour is 1:40-1:3;
(3) aniline is at copper coating in situ Polymerization
Aniline monomer and copper modification silica flour are carried out to ultrasonic blend in the acid solution system of Bronsted acid, then add ammonium persulfate, carry out in-situ polymerization, use the alternately rear suction filtration of washing, the vacuumize of distilled water and ethanol, obtain functional amido silicon based anode material; Wherein: the mass ratio of ammonium persulfate and aniline is 1:2-1:4, the mass ratio of copper modification silica flour and aniline is 4:1-1:1.
2. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (1), the particle size interval scope of silica flour is between 20 to 8000nm.
3. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (1), copper sulfate solution concentration is 1.5-15g/L.
4. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (1), ultrasonic power is 1.5-2w/cm, and supersonic frequency is 20-30kHz, and ultrasonic time is 0.5-1h.
5. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (2), sodium borohydride aqueous solution concentration is 0.9-9g/L, and time for adding is 1-5min, and the reaction time is 5-10min.
6. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (2), vacuumize temperature is 45-55 DEG C, and the vacuumize time is 10-12 h.
7. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (3), polymeric reaction temperature is 0-10 DEG C, and polymerization reaction time is 4-10 h.
8. the preparation method of functional amido silicon based anode material according to claim 1, it is characterized in that in described step (3), Bronsted acid is one or more the mixture in hydrochloric acid, DBSA, camphorsulfonic acid, p-methyl benzenesulfonic acid, pyrovinic acid, normal-butyl/ethyl phosphonic acid, n-decane base phosphoric acid, benzyl phosphoric acid, benzoic acid.
9. the preparation method of functional amido silicon based anode material according to claim 1, is characterized in that, in described step (3), vacuumize temperature is 50-60 DEG C, and the vacuumize time is 10-12 h.
10. the functional amido silicon based anode material that prepared by claim 1-9 either method is entrained in the application as lithium ion battery negative material in graphite.
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| CN108206285A (en) * | 2017-12-12 | 2018-06-26 | 中国科学院物理研究所 | A kind of nanometer tin negative pole material of compound coating and its preparation method and application |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
| CN110931727A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Preparation method of conductive polymer-coated silicon-based negative electrode material |
| CN111384369A (en) * | 2018-12-29 | 2020-07-07 | 北方奥钛纳米技术有限公司 | Negative electrode material and preparation method thereof, manufacturing method of negative electrode piece and lithium ion battery |
| CN113394402A (en) * | 2021-07-01 | 2021-09-14 | 安徽科达新材料有限公司 | Morphology-controllable spherical graphite negative electrode material and preparation method thereof |
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| 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 |
| CN108206285A (en) * | 2017-12-12 | 2018-06-26 | 中国科学院物理研究所 | A kind of nanometer tin negative pole material of compound coating and its preparation method and application |
| CN108206285B (en) * | 2017-12-12 | 2021-08-24 | 中国科学院物理研究所 | Composite coated nano tin anode material and preparation method and application 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 |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
| CN111384369A (en) * | 2018-12-29 | 2020-07-07 | 北方奥钛纳米技术有限公司 | Negative electrode material and preparation method thereof, manufacturing method of negative electrode piece and lithium ion battery |
| CN110931727A (en) * | 2019-10-25 | 2020-03-27 | 合肥国轩高科动力能源有限公司 | Preparation method of conductive polymer-coated silicon-based negative electrode material |
| CN113394402A (en) * | 2021-07-01 | 2021-09-14 | 安徽科达新材料有限公司 | Morphology-controllable spherical graphite negative electrode material and preparation method thereof |
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