CN105019015A - Electrochemical preparation method of amorphous silica material - Google Patents
Electrochemical preparation method of amorphous silica material Download PDFInfo
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- CN105019015A CN105019015A CN201510399383.9A CN201510399383A CN105019015A CN 105019015 A CN105019015 A CN 105019015A CN 201510399383 A CN201510399383 A CN 201510399383A CN 105019015 A CN105019015 A CN 105019015A
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- lithium
- silicon
- silica flour
- amorphous silica
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Abstract
The invention relates to an electrochemical preparation method of an amorphous silica material. The method comprises the following steps: using a silicon source to prepare an electrode plate as a negative pole, using a lithium source as a positive pole, using an organic solvent containing lithium salt as an electrolyte solution, performing constant-current discharge under the control of an external circuit, moving lithium ions to the negative pole from the positive pole, forming an alloy with silicon, and then performing constant-current and constant-voltage charge to be 3V when the potential difference on both sides is 0.001 V, stopping, taking out the silicon electrode, washing and performing low-temperature sintering to obtain the amorphous silica material. The amorphous silica material prepared by the method has the characteristics of safety, environmental protection, simple technology, low cost and large-scale production; and the amorphous silica material prepared by the method can be used for hydrogen storage materials, and can also be applied to lithium ion battery cathode materials and other fields using amorphous silica.
Description
Technical field
The present invention relates to a kind of preparation method of unformed silicon materials, more particularly relate to a kind of electrochemical method that a kind of crystalline silicon powder prepares unformed silicon materials, product can be used in the fields such as lithium ion cell high-capacity negative material, hydrogen storage material.
Background technology
Unformed silicon has very large advantage than crystalline silicon in some aspects, and such as in Chu Qing field, unformed silicon can absorb the hydrogen of 18-50 atom %, and this result once caused hydrogen storage material area research person great interest.Unformed silicium cathode material also grows to even greater heights in the research of field of lithium ion battery, after the embedding lithium of unformed silicium cathode material film, ensure the elastic reaction of lithium ion completely reversibility, these silicon fimls have enough stress relief abilities, and can not produce interconnective crack.The silicon based anode material of undefined structure has good capacity than the silicium cathode material of corresponding crystalline structure and keeps and cycle life.
Current unformed silicon materials preparation is mainly passed through
chemical reaction method, utilize
silicon halide and MAGNESIUM METAL are reacted or the method for CVD,
these method costs are high, dangerous large, and are not suitable for scale operation.The present invention utilizes electrochemical method, by crystalline silicon through embedding lithium, de-lithium circulation once or several times, obtains unformed silicon materials, in this electrochemical reaction process
lithium, can Reusability just as a kind of structure deteriorate agent.the method, compared with chemical process, simple, safety, environmental protection, to be produced on a large scale.Namely its product can be used in field of lithium ion battery also can in unformed silicon Application Areass such as hydrogen storage materials.
Summary of the invention
The object of the invention is to provide a kind of electrochemical preparation method of unformed silicon, it is characterized in that having following technological process and step:
A makes cathode electrode sheet: get a certain amount of silica flour, binding agent and conductive agent even by liquid-phase mixing, then be coated on Copper Foil, foam copper or stainless steel conducting base, through oven dry, roll extrusion, vacuum-drying is placed on humidity and is less than in the environment of 1%RH for subsequent use.The mass percent of described silica flour, binding agent, conductive agent is: silica flour 60 ~ 90%, binding agent 5 ~ 20%, conductive agent 5 ~ 20%;
It is anode that b gets lithium, using containing the organic solvent of lithium salts as electrolytic solution, with polyethylene or polyacrylic porous-film for barrier film, be assembled into battery under an inert atmosphere;
C controls to carry out constant-current discharge by external circuit, lithium ion shifts to negative electrode by anode, and forms Li-Si alloy with silicon, when both sides potential difference is 0.001V, carry out constant-current constant-voltage charging again to 3V, Li-Si alloy carries out removal alloying, and lithium is deviate from, at this moment, the crystalline structure of silicon is destroyed, become undefined structure, in order to ensure the partial amorphism degree of silicon, 1 ~ 10 time so repeatedly; Cathode sheets with silica flour taken out, with deionized water wash, 80 ~ 150 DEG C of vacuum-drying 24h, low temperature 200 ~ 500 DEG C sintering 2-8h, except no-bonder and conductive agent, obtains unformed silicon materials.
Above-mentioned silica flour is the silica flour receiving a micron silica flour, surperficial bag carbon with crystalline structure, or silicon alloy powder, size range 5nm ~ 3um; Described lithium source is any one in pure lithium or lithium alloy; Binding agent comprises polyvinylidene difluoride (PVDF) (PVDF) or Xylo-Mucine or SBR emulsion or polyacrylic acid, or any one in polyacrylic ester; Conductive agent comprises any one in carbon black or acetylene black or Ketjen black; Containing the organic electrolyte of lithium salts, wherein, solvent comprises any one or its combination in linear carbonate or cyclic carbonate or ethers; Lithium salts comprises lithium perchlorate, or trifluoromethane sulfonic acid imine lithium, LiBF4, any one or combination in lithium hexafluoro phosphate; Lithium salts concentration is in the electrolytic solution 0.2 ~ 2mol/L.
The feature of the inventive method is can continuous seepage, at silicon electrode by after electrochemical reaction partial amorphism, and the new cathode electrode of replaceable another one,
lithium is just as the structure deteriorate agent of silicon, and do not consume in theory, lithium anode can repeatedly use.Wherein, controlling size of current can determine according to the content of silica flour in cathode sheets, usually calculates according to the theoretical capacity of silicon,
C (theoretical capacity)=m(silica flour quality g) × 4200mAh/g,
Electric current can be followed and be controlled in following scope according to needs:
I(mA)=(0.01~0.2)C/1h 。
Accompanying drawing explanation
Fig. 1 is the schematic diagram of electrochemical preparation method of the present invention.
Embodiment
By the following examples content of the present invention is described further.
Embodiment 1
Under an inert atmosphere, 0.15g PVDF binding agent is dissolved in nitrogen methyl-2-pyrrolidone, then add 0.75g silica flour successively, 0.1g acetylene black mixes, slurry is coated in foam copper current collector.First dry in a conventional oven, except desolventizing, then, the solvent of vacuum-drying removing trace and moisture content, compare 0.9g/cm according to compacting
3roll extrusion to required thickness, then using this sheet material as negative electrode, Lithium sheet is anode, and lithium sheet is more bigger than silicon positive plate size, with 0.5M LiClO
4nSC 11801, methylcarbonate and glycol dimethyl ether (volume ratio 1:3:1) be ionogen, three layers of porous PP/PE/PP are barrier film (voidage 50%), battery is assembled in argon gas atmosphere, with the current discharge of 0.1C multiplying power to 0.001V, then 3.0V is charged to, 3 times so repeatedly, negative electrode is taken out, with deionized water wash, centrifugal settling or suction filtration, repeatedly several times, remove remaining lithium ion, vacuum 200 DEG C of dry 3h, carry out sintering 2h in 500 DEG C of air, just obtain unformed silicon powder material.
Embodiment 2
Under an inert atmosphere, 0.15g PAA (polyacrylic acid) binding agent is dissolved in deionized water, then adds the silica flour of 0.85g coated with carbon successively, Homogeneous phase mixing slurry is coated on Copper Foil.First dry in a conventional oven, except desolventizing, the solvent of last vacuum-drying removing trace and moisture content, according to the thickness that compacting is extremely more required than 0.9 roll extrusion, then using this sheet material as negative electrode, Lithium sheet is anode, lithium anode chip size is more bigger than silicon cathode sheets size, with 0.5M LiPF
6nSC 11801, r-fourth Inner ester, diethyl carbonate (volume ratio 1:1:1) be ionogen, three layers of porous PP/PE/PP are barrier film (voidage 50%), battery is assembled in argon gas atmosphere, with the current discharge of 0.01C multiplying power to 0.001V, then 3.0V is charged to, 3 times so repeatedly, negative electrode is taken out, with deionized water wash, centrifugal settling or suction filtration, repeatedly several times, removing lithium ion, vacuum 200 DEG C of dry 3h, carry out sintering 5h in 400 DEG C of air, just obtain unformed silicon powder material.
Embodiment 3
Under an inert atmosphere, 0.15g CMC binding agent is dissolved in deionized water, then adds 0.75g silica flour successively, 0.1g Ketjen black, Homogeneous phase mixing, finally slurry is coated on stainless steel collector.First dry in a conventional oven, except desolventizing, the solvent of vacuum-drying removing trace and moisture content, according to the thickness that compacting is extremely more required than 0.9 roll extrusion, then using this sheet material as negative electrode, Lithium sheet is anode, lithium anode chip size is more bigger than silicon cathode sheets size, to contain 0.2M Li [N (CF
3)
2sO
3], the methylcarbonate of 0.1M, diethyl carbonate, (volume ratio 1:1:1) are ionogen, three layers of porous PP/PE/PP are barrier film (voidage 50%), battery is assembled in argon gas atmosphere, with the current discharge of 0.05C multiplying power to 0.001V, then 3.0V is charged to, 3 times so repeatedly, negative electrode is taken out, with deionized water wash, centrifugal settling or suction filtration, repeatedly several times, removing lithium ion, vacuum 200 DEG C of dry 3h, in 600 DEG C of air, carry out sintering 0.5h, just obtain unformed silicon powder material.
Claims (5)
1. an electrochemical preparation method for unformed silicon materials, is characterized in that having following technological process and step:
A makes cathode electrode sheet: get a certain amount of crystal silica flour, binding agent and conductive agent, even by liquid-phase mixing, then be coated on Copper Foil, foam copper or stainless steel conducting base, through oven dry, roll extrusion, vacuum-drying is placed on humidity and is less than in the environment of 1%RH for subsequent use; The mass percent of described silica flour, binding agent, conductive agent is: silica flour 60 ~ 90%, binding agent 5 ~ 20%, conductive agent 5 ~ 20%;
It is anode that b gets lithium, using containing the organic solvent of lithium salts as electrolytic solution, with polyethylene or polyacrylic porous-film for barrier film, be assembled into battery under an inert atmosphere;
C controls to carry out constant-current discharge by external circuit, and lithium ion shifts to negative electrode by anode, and forms alloy with silicon, when both sides potential difference is 0.001V, then carries out constant-current constant-voltage charging to 3V, 1 ~ 10 time so repeatedly; Cathode sheets with silica flour taken out, with deionized water wash, 80 ~ 150 DEG C of vacuum-drying 24h, low temperature 200 ~ 500 DEG C sintering 2-8h, except no-bonder and conductive agent, obtains unformed silicon materials.
2., according to the electrochemical preparation method of a kind of unformed silicon described in claim 1, it is characterized in that described silica flour is the silica flour receiving a micron silica flour, surperficial bag carbon with crystalline structure, or silicon alloy powder, size range 5nm ~ 3um; Described lithium source is any one in pure lithium or lithium alloy.
3. according to the electrochemical preparation method of a kind of unformed silicon described in claim 1, it is characterized in that binding agent comprises polyvinylidene difluoride (PVDF) (PVDF) or Xylo-Mucine or SBR emulsion or polyacrylic acid, or any one in polyacrylic ester.
4., according to the electrochemical preparation method of a kind of unformed silicon described in claim 1, it is characterized in that any one that conductive agent comprises in carbon black or acetylene black or Ketjen black.
5. according to the electrochemical preparation method of a kind of unformed silicon described in claim 1, it is characterized in that the described organic electrolyte containing lithium salts, wherein, solvent comprises any one or its combination in linear carbonate or cyclic carbonate or ethers; Lithium salts comprises lithium perchlorate, or trifluoromethane sulfonic acid imine lithium, LiBF4, any one or combination in lithium hexafluoro phosphate; Lithium salts concentration is in the electrolytic solution 0.2 ~ 2mol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107086294A (en) * | 2017-04-24 | 2017-08-22 | 广东烛光新能源科技有限公司 | A kind of preparation method of nano silica-base material |
| CN107093738A (en) * | 2017-04-24 | 2017-08-25 | 广东烛光新能源科技有限公司 | A kind of preparation method of nano silica-base material |
| CN107093737A (en) * | 2017-04-24 | 2017-08-25 | 广东烛光新能源科技有限公司 | A kind of preparation method of nano silica-base material |
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| CN107093738A (en) * | 2017-04-24 | 2017-08-25 | 广东烛光新能源科技有限公司 | A kind of preparation method of nano silica-base material |
| CN107093737A (en) * | 2017-04-24 | 2017-08-25 | 广东烛光新能源科技有限公司 | A kind of preparation method of nano silica-base material |
| CN107093737B (en) * | 2017-04-24 | 2019-11-05 | 广东烛光新能源科技有限公司 | A kind of preparation method of nano silica-base material |
| CN107093738B (en) * | 2017-04-24 | 2019-12-24 | 广东烛光新能源科技有限公司 | Preparation method of nano silicon-based material |
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Application publication date: 20151104 |