CN108493392A - A kind of method of Li-Si alloy surface fluorination - Google Patents
A kind of method of Li-Si alloy surface fluorination Download PDFInfo
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- CN108493392A CN108493392A CN201810076535.5A CN201810076535A CN108493392A CN 108493392 A CN108493392 A CN 108493392A CN 201810076535 A CN201810076535 A CN 201810076535A CN 108493392 A CN108493392 A CN 108493392A
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- Prior art keywords
- alloy
- negative plate
- silicon
- battery
- pole
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of method of Li-Si alloy surface fluorination, as follows：（1）Silicon slurry is uniformly coated on copper foil by coating machine, it is that button half-cell is assembled into pole with lithium piece with silicon pole piece for a pole in glove box, discharge treatment is carried out to battery in battery testing cabinet, then dismantles half-cell in glove box and takes out Li-Si alloy negative plate；（2）Suitable perfluorinated resin is taken to be placed in quartz curette bottom, on quartz curette top by stainless (steel) wire by step（1）In Li-Si alloy negative plate separated with perfluorinated resin, place into the Li-Si alloy negative plate that heating and thermal insulation in tube furnace forms surface cladding lithium fluoride.The present invention carries out prelithiation by way of charge discharge to silicon pole piece, forms Li-Si alloy pole piece, then carry out fluorination treatment, when applied to battery electrode, to improve the first effect and stable circulation performance of battery.Method simple possible, and effectively solve the problems, such as of the existing technology.
Description
Technical field
The present invention relates to a kind of methods of Li-Si alloy surface fluorination.
Background technology
For lithium silion cell, silicon face is difficult to form stable surface solid electrolyte（SEI）Film, when removal lithium embedded, are huge
The silicon face electrolyte that big volume change causes SEI films to be destroyed, and newly expose continues to be decomposed to form new SEI films,
Cycle goes down to cause SEI films more and more thicker, and efficiency for charge-discharge reduces, electrolyte consumption, and then internal resistance increases, under cycle performance
Drop, thus it is particularly important to the advance benefit lithium of lithium silion cell cathode.Meanwhile the degree of lithium silion cell prelithiation is largely
Battery performance is influenced, prelithiation degree is too low, limited to lithium silion cell performance boost, and prelithiation degree is excessively high, excessive lithium meeting
Dendritic crystal is formed, diaphragm and electrode surface can be destroyed.Have it is demonstrated experimentally that lithium fluoride can effectively prevent the formation of Li dendrite, energy
The effective uniformity and corrosion resistance for improving electrode surface.
Invention content
The purpose of the present invention is being directed to these problems and theory, a kind of method of Li-Si alloy surface fluorination is proposed.To silicon
Negative material pre-embedding lithium processes form Li-Si alloy, then carry out surface fluorination processing, and forming fine and close lithium fluoride in silicon face protects
Cuticula, this can effectively solve the problem that the first effect and stable circulation performance problem of lithium silion cell.
The present invention is achieved by the following technical solutions.
A kind of method of Li-Si alloy surface fluorination of the present invention, as follows.
（1）Silicon slurry is uniformly coated on copper foil by coating machine, with silicon pole piece for a pole in glove box, with lithium
Piece is to be assembled into button half-cell to pole, carries out discharge treatment to battery in battery testing cabinet, then half is dismantled in glove box
Battery takes out Li-Si alloy negative plate.
（2）Suitable perfluorinated resin is taken to be placed in quartz curette bottom, on quartz curette top by stainless (steel) wire by step（1）In
Li-Si alloy negative plate separated with perfluorinated resin, place into the lithium silicon that heating and thermal insulation in tube furnace forms surface cladding lithium fluoride
Alloy anode piece.
The Li-Si alloy negative plate of advance lithiumation, which carries out fluorination treatment, to form one layer of cause on Li-Si alloy negative plate surface
Close lithium fluoride protective film can effectively improve the uniformity and corrosion resistance of Li-Si alloy negative terminal surface in charge and discharge process.
The present invention by way of charge discharge to silicon pole piece carry out prelithiation, formed Li-Si alloy pole piece, then into
Row fluorination treatment, when applied to battery electrode, to improve the first effect and stable circulation performance of battery.Method simple possible, and
It effectively solves the problems, such as of the existing technology.
Specific implementation mode
The present invention will be described further by following embodiment.But the present invention is not limited to following embodiments.
Embodiment 1.
A certain amount of active material silicon and conductive agent are weighed, with 200 r/min rotating speeds ball milling 2 in planetary ball mill
Appropriate N-Methyl pyrrolidone (NMP is added in h）Solution, ultrasonic 40min；With 10000 r/min high speed shears 40 in FA25
Li-Si alloy slurry is made in min, and uniformly slurry 100um thickness is coated on copper foil with coating machine, is dried in 60 DEG C of drying boxes
The pole piece of φ 14mm is cut into get to Li-Si alloy negative plate.With silicon pole piece for a pole in the glove box full of argon gas, with lithium
Piece is to be assembled into button half-cell to pole, and discharge treatment is carried out to battery in battery testing cabinet, and control discharge capacity is
1200mAh/g, then dismantle half-cell in glove box and take out Li-Si alloy negative plate.Suitable perfluorinated resin is taken to be placed in quartz curette
Li-Si alloy negative plate is separated by stainless (steel) wire with perfluorinated resin on quartz curette top, is being continually fed into nitrogen by bottom
It is heated to 350 DEG C in tube furnace and keeps the temperature 2 hours, then cools to 150 DEG C and keeps the temperature 12 hours to get the lithium of lithium fluoride is coated to surface
Silicon alloy negative plate.
Embodiment 2.
A certain amount of active material silicon and conductive agent are weighed, with 200 r/min rotating speeds ball milling 1 in planetary ball mill
Appropriate N-Methyl pyrrolidone (NMP is added in h）Solution, ultrasonic 20min；With 10000 r/min high speed shears 60 in FA25
Li-Si alloy slurry is made in min, and uniformly slurry 100um thickness is coated on copper foil with coating machine, is dried in 60 DEG C of drying boxes
The pole piece of φ 14mm is cut into get to Li-Si alloy negative plate.With silicon pole piece for a pole in the glove box full of argon gas, with lithium
Piece is to be assembled into button half-cell to pole, and discharge treatment is carried out to battery in battery testing cabinet, and control discharge capacity is
1000mAh/g, then dismantle half-cell in glove box and take out Li-Si alloy negative plate.Suitable perfluorinated resin is taken to be placed in quartz curette
Li-Si alloy negative plate is separated by stainless (steel) wire with perfluorinated resin on quartz curette top, is being continually fed into nitrogen by bottom
It is heated to 350 DEG C in tube furnace and keeps the temperature 2 hours, then cools to 175 DEG C and keeps the temperature 10 hours to get the lithium of lithium fluoride is coated to surface
Silicon alloy negative plate.
Claims (1)
1. a kind of method of Li-Si alloy surface fluorination, it is characterized in that as follows：
（1）Silicon slurry is uniformly coated on copper foil by coating machine, is with lithium piece for a pole with silicon pole piece in glove box
To pole, it is assembled into button half-cell, discharge treatment is carried out to battery in battery testing cabinet, then dismantle half-cell in glove box
Take out Li-Si alloy negative plate；
（2）Suitable perfluorinated resin is taken to be placed in quartz curette bottom, on quartz curette top by stainless (steel) wire by step（1）In lithium
Silicon alloy negative plate is separated with perfluorinated resin, places into the Li-Si alloy that heating and thermal insulation in tube furnace forms surface cladding lithium fluoride
Negative plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810076535.5A CN108493392A (en) | 2018-01-26 | 2018-01-26 | A kind of method of Li-Si alloy surface fluorination |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810076535.5A CN108493392A (en) | 2018-01-26 | 2018-01-26 | A kind of method of Li-Si alloy surface fluorination |
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| CN108493392A true CN108493392A (en) | 2018-09-04 |
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| CN201810076535.5A Pending CN108493392A (en) | 2018-01-26 | 2018-01-26 | A kind of method of Li-Si alloy surface fluorination |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461911A (en) * | 2018-10-22 | 2019-03-12 | 江西省科学院科技战略研究所(江西省科学院科技信息中心) | A kind of cladded type Li-Si alloy and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102612776A (en) * | 2009-11-05 | 2012-07-25 | 尤米科尔公司 | Core-shell lithium transition metal oxides |
| CN102694158A (en) * | 2012-06-13 | 2012-09-26 | 上海空间电源研究所 | Silicon-containing lithium cathode, preparation method thereof and lithium sulfur battery with silicon-containing lithium cathode |
| CN105374571A (en) * | 2014-08-26 | 2016-03-02 | 万星光电子(东莞)有限公司 | Lithium ion capacitor negative electrode sheet, preparation method thereof, and winding-type lithium ion capacitor |
| CN105789555A (en) * | 2016-04-26 | 2016-07-20 | 中国科学院长春应用化学研究所 | Silicon composite material and preparation method thereof as well as battery cathode and lithium ion battery |
-
2018
- 2018-01-26 CN CN201810076535.5A patent/CN108493392A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102612776A (en) * | 2009-11-05 | 2012-07-25 | 尤米科尔公司 | Core-shell lithium transition metal oxides |
| CN102694158A (en) * | 2012-06-13 | 2012-09-26 | 上海空间电源研究所 | Silicon-containing lithium cathode, preparation method thereof and lithium sulfur battery with silicon-containing lithium cathode |
| CN105374571A (en) * | 2014-08-26 | 2016-03-02 | 万星光电子(东莞)有限公司 | Lithium ion capacitor negative electrode sheet, preparation method thereof, and winding-type lithium ion capacitor |
| CN105789555A (en) * | 2016-04-26 | 2016-07-20 | 中国科学院长春应用化学研究所 | Silicon composite material and preparation method thereof as well as battery cathode and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| JIE ZHAO等: "Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461911A (en) * | 2018-10-22 | 2019-03-12 | 江西省科学院科技战略研究所(江西省科学院科技信息中心) | A kind of cladded type Li-Si alloy and its preparation method and application |
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Application publication date: 20180904 |