CN115188919B - Negative plate, preparation method thereof and battery - Google Patents
Negative plate, preparation method thereof and battery Download PDFInfo
- Publication number
- CN115188919B CN115188919B CN202211009709.9A CN202211009709A CN115188919B CN 115188919 B CN115188919 B CN 115188919B CN 202211009709 A CN202211009709 A CN 202211009709A CN 115188919 B CN115188919 B CN 115188919B
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- silicon
- layer
- electrode material
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 98
- 239000002131 composite material Substances 0.000 claims abstract description 86
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 75
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 68
- 239000010703 silicon Substances 0.000 claims abstract description 68
- 239000007773 negative electrode material Substances 0.000 claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010041 electrostatic spinning Methods 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 30
- 239000010405 anode material Substances 0.000 claims description 23
- 239000002923 metal particle Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- 239000011863 silicon-based powder Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000004584 polyacrylic acid Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910021426 porous silicon Inorganic materials 0.000 claims description 3
- 239000002620 silicon nanotube Substances 0.000 claims description 3
- 229910021430 silicon nanotube Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 18
- 239000011889 copper foil Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 208000012886 Vertigo Diseases 0.000 description 4
- 238000007606 doctor blade method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920005594 polymer fiber Polymers 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- 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
-
- 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
- H01M4/0414—Methods of deposition of the material by screen printing
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a negative plate, a preparation method thereof and a battery. The negative electrode plate comprises a current collector, and a lithium metal layer and a composite silicon negative electrode layer which are sequentially laminated on at least one surface of the current collector, wherein the composite silicon negative electrode layer is composed of a negative electrode material and a fiber layer embedded in the negative electrode material, and the negative electrode material comprises a silicon-based negative electrode material. The negative electrode plate not only relieves the problem of capacity attenuation of the silicon-based negative electrode material caused by volume expansion, but also relieves the problems that lithium dendrite is easy to generate in lithium metal and side reaction occurs with an electrolyte layer, and meanwhile, through multiplexing of the lithium metal layer and the composite silicon negative electrode layer, the electrochemical performance of the battery is remarkably improved, and particularly the energy density of the battery is remarkably improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative plate, a preparation method thereof and a battery.
Background
With the continuous development of lithium ion battery technology, lithium ion batteries have been widely used in the fields of portable electronic products (such as notebook computers, mobile phones and digital cameras) and electric automobiles. Because of the rapid updating of related electric equipment, the related field puts higher requirements on the energy density of the lithium ion battery. However, the current commercial lithium ion battery cathode material is mainly graphite, and the graphite has low energy density (372 mAh/g) and is difficult to meet the requirement of high energy density.
The silicon-based anode material has higher theoretical specific capacity (4200 mAh/g), is an ideal substitute material for graphite anode materials, however, the silicon-based anode material can have huge volume expansion in the charge and discharge process, the volume change exceeds 400%, the crushing, pulverization and stripping of the anode material can be caused, the rapid attenuation of the capacity is finally caused, and the defects limit the large-scale application of the silicon anode.
Meanwhile, lithium metal is also an ideal negative electrode material due to the higher theoretical capacity (3860 mAh/g) and lower potential. However, in a battery using lithium metal as a negative electrode, uneven deposition of lithium ions may cause formation of lithium dendrites, penetration of an electrolyte membrane may cause short circuit of the battery with increase of cycle number, and compatibility of the lithium metal negative electrode and a solid electrolyte is poor, and direct contact of metal lithium and the solid electrolyte may cause side reactions, which may consume lithium metal, increase internal resistance of the battery, and eventually cause deterioration of electrical performance of the battery.
Therefore, the silicon-based negative electrode material and the lithium metal negative electrode material in the related art have respective defects, resulting in poor electrical properties of the silicon-based negative electrode lithium ion battery and the lithium metal negative electrode lithium ion battery.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of poor electrical performance of the silicon-based negative electrode lithium ion battery and the lithium metal negative electrode lithium ion battery in the prior art, thereby providing a negative electrode sheet, a preparation method thereof and a battery.
For this purpose, the invention provides a negative electrode sheet, which comprises a current collector, and a lithium metal layer and a composite silicon negative electrode layer which are sequentially laminated on at least one surface of the current collector, wherein the composite silicon negative electrode layer consists of a negative electrode material and a fiber layer embedded in the negative electrode material, the negative electrode material comprises a silicon-based negative electrode material, and metal particles are loaded in the fiber layer.
Optionally, the thickness of the lithium metal layer is 20-80 μm, the thickness of the composite silicon anode layer is 10-50 μm, and the thickness of the fiber layer in the composite silicon anode layer is 5-20 μm;
optionally, the ratio of the thickness of the lithium metal layer to the thickness of the composite silicon anode layer is (1-3): 1-2;
optionally, the weight ratio of the lithium metal layer to the composite silicon anode layer is (1-5): 1-2.
Optionally, the weight percentage of the silicon-based anode material is 90-99 wt% based on the total weight of the anode material;
optionally, the negative electrode material further comprises a conductive agent and a binder, wherein the weight percentage of the conductive agent is 0.5-5 wt% based on the total weight of the negative electrode material, and the weight percentage of the binder is 0.5-5 wt%;
optionally, the silicon-based anode material is at least one selected from silicon powder, silicon oxide, a silicon film, a silicon nanowire, a silicon nanotube, porous silicon and hollow silicon; the conductive agent is at least one selected from carbon nanotubes, acetylene black, carbon fibers, ketjen black and conductive carbon black; the binder is at least one selected from polyacrylic acid, polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and sodium alginate. The silicon oxide may be, for example, silicon oxide or non-stoichiometric SiO x 。
Optionally, the fiber layer includes an electrospun fiber layer including electrospun fibers, and the metal particles are supported in the electrospun fibers.
Optionally, the diameter of the electrostatic spinning fiber is 3-10 mu m, and the particle size of the metal particles is 50-200 nm;
optionally, the electrospun fiber is prepared from a polymer raw material, wherein the polymer raw material is at least one selected from polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), polycaprolactone (PCL) and polymethyl methacrylate (PMMA);
optionally, the metal particles are selected from at least one of silver, gold, copper, aluminum, indium, germanium, sodium, magnesium, chromium, titanium, barium, nickel, molybdenum, cobalt, platinum, zinc, iron, tin, bismuth, and antimony;
optionally, in the electrospun fiber, the weight ratio of the polymer raw material to the metal particles is (2-5): 1.
Alternatively, the current collector may be selected within a certain range, for example, the current collector may be a copper foil having a thickness of 10 μm.
The invention also provides a method for preparing the negative plate, which comprises the following operations:
coating the anode material slurry on one surface of a fiber layer, and drying to obtain an anode material-fiber composite sheet; the negative electrode material slurry contains a silicon-based negative electrode material, the negative electrode material-fiber composite sheet consists of a negative electrode material and a fiber layer embedded in the negative electrode material, and metal particles are loaded in the fiber layer;
and arranging the negative electrode material-fiber composite sheet opposite to the lithium metal surface of the lithium metal-current collector composite sheet, and pressing.
When the anode material slurry is coated on one surface of the fiber layer, the anode material slurry gradually infiltrates the fiber layer after being coated on the surface of the fiber layer due to fluidity, and finally completely coats the fiber layer, and the anode material embedded fiber layer structure is formed after drying.
Optionally, the solid content of the anode material slurry is 20-50%, the anode material slurry further contains a conductive agent and a binder, the weight percentage of the silicon-based anode material is 90-99% by weight based on the total weight of the dry basis of the solid components in the anode material slurry, the weight percentage of the conductive agent is 0.5-5% by weight, and the weight percentage of the binder is 0.5-5% by weight.
Optionally, the silicon-based anode material is at least one selected from silicon powder, silicon oxide, a silicon film, a silicon nanowire, a silicon nanotube, porous silicon and hollow silicon; the conductive agent is at least one selected from carbon nanotubes, acetylene black, carbon fibers, ketjen black and conductive carbon black (Super-P); the binder is at least one selected from polyacrylic acid, polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and sodium alginate.
Alternatively, when the anode material slurry is coated on one surface of the fiber layer, the coating thickness of the anode material slurry is 20 to 70 μm, and the thickness of the fiber layer is 5 to 20 μm.
Optionally, when the negative electrode material-fiber composite sheet is obtained by drying, the drying temperature is 80-100 ℃ and the drying time is 8-12 h.
Optionally, the fiber layer is an electrostatic spinning fiber layer, the electrostatic spinning fiber layer comprises electrostatic spinning fibers, and the metal particles are loaded in the electrostatic spinning fibers; the preparation process of the electrostatic spinning fiber layer comprises the following steps: taking a polymer raw material, and dissolving the polymer raw material in a solvent to obtain a polymer solution; adding the metal particles into the polymer solution, and uniformly dispersing to obtain a composite fluid; and taking the composite fluid, carrying out electrostatic spinning treatment and drying.
Optionally, when the product subjected to electrostatic spinning treatment is dried, the drying temperature is 60-100 ℃ and the drying time is 4-12 h.
Optionally, the solvent is selected from at least one of N, N-dimethylformamide, deionized water, tetrahydrofuran, acetone, and N, N-dimethylacetamide.
Optionally, the polymer raw material is selected from at least one of polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), polycaprolactone (PCL) and polymethyl methacrylate (PMMA).
Optionally, the metal particles are selected from at least one of silver, gold, copper, aluminum, indium, germanium, sodium, magnesium, chromium, titanium, barium, nickel, molybdenum, cobalt, platinum, zinc, iron, tin, bismuth, and antimony; the particle size of the metal particles is 50-200 nm.
Optionally, the concentration of the polymer raw material in the polymer solution is 0.1-0.2 g/mL.
Optionally, in the composite fluid, the weight ratio of the polymer raw material to the metal particles is (2-5): 1.
Optionally, the conditions of the electrospinning process include: the flow rate of the composite fluid is 0.009-0.02 mL/min, the voltage is 10-20 Kv, the collecting distance is 10-15 cm, the temperature is 20-30 ℃ and the time is 1-3 h.
Alternatively, the lithium metal-current collector composite sheet is composed of a current collector and lithium metal on one surface of the current collector.
Optionally, the current collector is copper foil; in the lithium metal-current collector composite sheet, the thickness of the current collector is 10 μm, and the thickness of the lithium metal is 20 to 80 μm.
The pressure of the pressing is 50-200 Mpa and the time is 3-10 min.
The invention also provides a battery, which comprises the negative plate.
Alternatively, the battery is any one of a liquid-phase lithium secondary battery, a semi-solid-state lithium secondary battery, and an all-solid-state lithium secondary battery.
The technical scheme of the invention has the following advantages:
(1) The negative electrode plate comprises a current collector, and a lithium metal layer and a composite silicon negative electrode layer which are sequentially laminated on at least one surface of the current collector, wherein the composite silicon negative electrode layer is composed of a negative electrode material and a fiber layer embedded in the negative electrode material, and the negative electrode material comprises a silicon-based negative electrode material. Firstly, a lithium metal layer and a composite silicon negative electrode layer containing a silicon-based negative electrode material are simultaneously arranged in the negative electrode plate, so that sufficient lithium sources can be provided, the first effect is improved, and the capacity density can be improved; secondly, the lithium metal layer is positioned between the current collector and the composite silicon negative electrode layer, so that lithium dendrites can be prevented from penetrating through an electrolyte membrane, and direct contact between lithium metal and the electrolyte layer can be effectively avoided, and side reactions of the lithium metal and the electrolyte layer are avoided; furthermore, the fiber layer is arranged in the composite silicon anode layer, and can provide a buffer space for the volume expansion of the silicon-based anode material in the composite silicon anode layer, so that the silicon anode layer is prevented from being broken, pulverized and peeled off due to the volume expansion.
Therefore, the negative electrode plate not only relieves the problem of capacity attenuation of the silicon-based negative electrode material caused by volume expansion, but also relieves the problems that lithium dendrite is easy to generate in lithium metal and side reaction occurs with an electrolyte layer, and meanwhile, through multiplexing of the lithium metal layer and the composite silicon negative electrode layer, the electrochemical performance of the battery is obviously improved, and particularly the energy density of the battery is obviously improved.
(2) According to the negative electrode plate provided by the invention, the metal particles are loaded in the fiber layer, so that the lithium ion conduction can be enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing SEM examination results of an electrospun fiber layer according to example 1 of the present invention;
fig. 2 is a schematic structural diagram of a negative electrode sheet prepared in example 1 of the present invention.
Reference numerals:
1. a current collector; 2. a lithium metal layer; 3. a composite silicon negative electrode layer; 301. a negative electrode material; 302. a fibrous layer.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a negative plate, which is prepared by the following method:
(1) Preparation of a fiber layer:
0.632g of Polyacrylonitrile (PAN) is weighed and dissolved in 6mL of N, N-Dimethylformamide (DMF), and the mixture is stirred and dissolved for 20min to obtain a polymer solution; adding 0.2g of nano silver particles (with the particle size of 100 nm) into the polymer solution, and magnetically stirring for 12 hours at room temperature to obtain a composite fluid; carrying out electrostatic spinning treatment on the composite fluid by using an electrostatic spinning device, wherein the flow rate of the composite fluid is 0.009mL/min, the voltage is set to 15Kv, the collecting distance between a transmitting needle head and a collector is 12cm, the temperature is 20 ℃, and the spinning time is 3h; after the electrostatic spinning treatment, the collected polymer fibers were dried at 100℃for 12 hours to obtain an electrostatic spinning fiber layer having a thickness of 10. Mu.m, and SEM test results thereof were shown in FIG. 1.
(2) Preparation of a negative electrode material-fiber composite sheet:
weighing 95g of silicon powder, 2.5g of carbon nanotube powder and 2.5g of polyacrylic acid, dispersing in a proper amount of deionized water, and stirring for 40min by using a vacuum stirrer to form uniform cathode material slurry with 42% of solid content; fixing the electrostatic spinning fiber layer prepared in the operation (1) on the surface of a PET substrate, and coating the negative electrode material slurry on the surface of the electrostatic spinning fiber layer in a doctor blade coating mode, wherein the coating thickness is 20 mu m; and after the coating is finished, drying the mixture in a vacuum oven at 100 ℃ for 12 hours, cooling the mixture, and removing the cooled mixture from the surface of the PET substrate to obtain the negative electrode material-fiber composite sheet, wherein the thickness of the negative electrode material-fiber composite sheet is 15 mu m.
(3) Preparing a negative electrode sheet:
and (3) taking a lithium metal-current collector composite sheet formed by compounding a copper foil and lithium metal (the thickness of a lithium layer is 30 microns, the thickness of a copper foil is 10 microns), arranging the negative electrode material-fiber composite sheet and the lithium metal surface of the lithium metal-current collector composite sheet oppositely, and then placing the negative electrode material-fiber composite sheet between pressing plates (10 cm multiplied by 10 cm) of a flat plate hot press, wherein the pressure is 100Mpa, and the pressure maintaining time is 5min, so that the negative electrode sheet of the embodiment is obtained.
As shown in fig. 2, the negative electrode sheet prepared in this example includes a current collector 1 (copper foil), and a lithium metal layer 2 and a composite silicon negative electrode layer 3 which are sequentially laminated on one surface of the current collector, the composite silicon negative electrode layer 3 being composed of a negative electrode material 301 and a fibrous layer 302 embedded in the negative electrode material.
Wherein the thickness of the lithium metal layer is 28 mu m, the thickness of the composite silicon anode layer is 14 mu m, and the ratio of the thickness of the lithium metal layer to the thickness of the composite silicon anode layer is 2:1, the weight ratio is 2.5:1, a step of; the negative electrode material contains 95 weight percent of silicon-based negative electrode material (silicon powder); the fiber layer is composed of electrostatic spinning fibers, nano silver particles are loaded in the electrostatic spinning fibers, the diameter of the electrostatic spinning fibers is 5 mu m, and the weight ratio of polymer raw materials (polyacrylonitrile) to the nano silver particles is 3.16:1.
example 2
A negative electrode sheet was prepared according to the method of example 1, except that the fiber layer in this example was prepared by the following steps:
0.703g of polyvinylidene fluoride (PVDF) is weighed and dissolved in 5mL of N, N-Dimethylacetamide (DMAC), and the mixture is stirred and dissolved for 20min to obtain a polymer solution; adding 0.2g of nano tin particles (with the particle size of 80 nm) into the polymer solution, and magnetically stirring for 12 hours at room temperature to obtain a composite fluid; carrying out electrostatic spinning treatment on the composite fluid by using an electrostatic spinning device, wherein the flow rate of the composite fluid is 0.016mL/min, the voltage is set to 15Kv, the collecting distance between a transmitting needle head and a collector is 15cm, the temperature is 20 ℃, and the spinning time is 3h; and after the electrostatic spinning treatment is finished, drying the collected polymer fibers at 100 ℃ for 12 hours to obtain an electrostatic spinning fiber layer, wherein the thickness of the electrostatic spinning fiber layer is 10 mu m.
In the negative electrode sheet prepared in this example, the fiber layer is composed of an electrospun fiber, nano tin particles are loaded in the electrospun fiber, the diameter of the electrospun fiber is 5 μm, wherein the weight ratio of the polymer raw material (polyvinylidene fluoride) to the nano tin particles is 3.515:1.
example 3
A negative electrode sheet was produced in the same manner as in example 1 except that the coating thickness of the negative electrode material slurry in operation (2) of this example was 40 μm, and the thickness of the resulting negative electrode material-fiber composite sheet was 30 μm; the pressing pressure in the operation (3) is 120Mpa and the time is 5min.
In the negative electrode sheet prepared in this example, the thickness of the lithium metal layer was 28 μm, the thickness of the composite silicon negative electrode layer was 28 μm, and the ratio of the thickness of the lithium metal layer to the thickness of the composite silicon negative electrode layer was 1:1, the weight ratio is 1.25:1.
example 4
A negative electrode sheet was produced in the same manner as in example 1 except that the coating thickness of the negative electrode material slurry in operation (2) of this example was 70 μm, and the thickness of the resulting negative electrode material-fiber composite sheet was 50 μm; the pressing pressure in the operation (3) is 150Mpa and the time is 3min.
In the negative electrode sheet prepared in this example, the thickness of the lithium metal layer was 28 μm, the thickness of the composite silicon negative electrode layer was 48 μm, and the ratio of the thickness of the lithium metal layer to the thickness of the composite silicon negative electrode layer was about 1:1.7, weight ratio of 1.25:1.7.
example 5
A negative electrode sheet was prepared in the same manner as in example 1, except that the silicon-based negative electrode material used in operation (2) of this example was silicon oxide.
Example 6
A negative electrode sheet was produced in the same manner as in example 1, except that in operation (2) of this example, the following steps were carried out: 5:5 weight ratio of silicon powder, carbon nanotube powder and polyacrylic acid.
Example 7
A negative electrode sheet was prepared in the same manner as in example 1, except that in the lithium metal-current collector composite sheet used in operation (3) of this example, the thickness of the lithium layer was 20 μm.
Example 8
A negative electrode sheet was prepared in the same manner as in example 1, except that in the lithium metal-current collector composite sheet used in operation (3) of this example, the thickness of the lithium layer was 80 μm.
Comparative example 1
The negative electrode sheet was prepared as follows:
(1) Preparation of a fiber layer:
0.632g of Polyacrylonitrile (PAN) is weighed and dissolved in 6mL of N, N-Dimethylformamide (DMF), and the mixture is stirred and dissolved for 20min to obtain a polymer solution; adding 0.2g of nano silver particles (with the particle size of 100 mu m) into the polymer solution, and magnetically stirring for 12 hours at room temperature to obtain a composite fluid; carrying out electrostatic spinning treatment on the composite fluid by using an electrostatic spinning device, wherein the flow rate of the composite fluid is 0.009mL/min, the voltage is set to 15Kv, the collecting distance between a transmitting needle head and a collector is 12cm, the temperature is 20 ℃, and the spinning time is 3h; and after the electrostatic spinning treatment is finished, drying the collected polymer fibers at 100 ℃ for 12 hours to obtain an electrostatic spinning fiber layer, wherein the thickness of the electrostatic spinning fiber layer is 10 mu m.
(2) Preparation of a negative electrode material-fiber composite sheet:
according to 95:2.5:2.5, weighing silicon powder, carbon nanotube powder and polyacrylic acid according to the weight ratio, dispersing the silicon powder, the carbon nanotube powder and the polyacrylic acid in a proper amount of deionized water, and stirring the mixture for 40 minutes by using a vacuum stirrer to form uniform anode material slurry with 42% of solid content; fixing the electrostatic spinning fiber layer prepared in the operation (1) on the surface of a PET substrate, and coating the negative electrode material slurry on the surface of the electrostatic spinning fiber layer in a doctor blade coating mode, wherein the coating thickness is 45 mu m; and after the coating is finished, drying the mixture in a vacuum oven at 100 ℃ for 12 hours, cooling the mixture, and removing the cooled mixture from the surface of the PET substrate to obtain the negative electrode material-fiber composite sheet, wherein the thickness of the negative electrode material-fiber composite sheet is 38 mu m.
(3) Preparing a negative electrode sheet:
and taking a copper foil (thickness is 10 microns), arranging the negative electrode material-fiber composite sheet and the copper foil oppositely, and then placing the copper foil between pressing plates (10 cm multiplied by 10 cm) of a flat plate hot press, and maintaining the pressure for 5min under 100Mpa to obtain the negative electrode sheet.
The negative electrode sheet prepared in this comparative example includes a current collector (copper foil), and a composite silicon negative electrode layer provided on one surface of the current collector, the composite silicon negative electrode layer being composed of a negative electrode material and a fibrous layer embedded in the negative electrode material, the thickness of the composite silicon negative electrode layer being 36 μm.
Comparative example 2
The negative electrode sheet was prepared as follows:
and taking a copper foil (with the thickness of 10 micrometers), and pressing a lithium metal layer with the thickness of 30 micrometers on the copper foil to obtain the negative plate.
Comparative example 3
The negative electrode sheet was prepared as follows:
(1) According to 90:2.5:2.5, weighing silicon powder, carbon nanotube powder and polyacrylic acid according to the weight ratio, dispersing the silicon powder, the carbon nanotube powder and the polyacrylic acid in a proper amount of deionized water, and stirring the mixture for 40 minutes by using a vacuum stirrer to form uniform anode material slurry with 42% of solid content;
(2) Taking a lithium metal-current collector composite sheet (a lithium layer: 30 micrometers, a copper foil: 10 micrometers) formed by compositing a copper foil sheet and lithium metal, and coating the negative electrode material slurry on a lithium metal surface of the lithium metal-current collector composite sheet in a doctor blade coating mode, wherein the coating thickness is 20 micrometers;
(3) And after the coating is finished, drying the mixture in a vacuum oven at 100 ℃ for 12 hours, and then placing the mixture between pressing plates (10 cm multiplied by 10 cm) of a flat plate hot press, and maintaining the pressure for 5 minutes at 100Mpa to obtain the negative plate.
Comparative example 4
The negative electrode sheet was prepared as follows:
(1) Preparation of a fiber layer:
0.632g of Polyacrylonitrile (PAN) is weighed and dissolved in 6mL of N, N-Dimethylformamide (DMF), and the mixture is stirred and dissolved for 20min to obtain a polymer solution; carrying out electrostatic spinning treatment on the polymer solution by using an electrostatic spinning device, wherein the flow rate of the polymer solution is 0.009mL/min, the voltage is set to 15Kv, the collecting distance between a transmitting needle head and a collector is 12cm, the temperature is 20 ℃, and the spinning time is 3h; and after the electrostatic spinning treatment is finished, drying the collected polymer fibers at 100 ℃ for 12 hours to obtain an electrostatic spinning fiber layer, wherein the thickness of the electrostatic spinning fiber layer is 10 mu m.
(2) Preparation of a negative electrode material-fiber composite sheet:
according to 90:2.5:2.5, weighing silicon powder, carbon nanotube powder and polyacrylic acid according to the weight ratio, dispersing the silicon powder, the carbon nanotube powder and the polyacrylic acid in a proper amount of deionized water, and stirring the mixture for 40 minutes by using a vacuum stirrer to form uniform anode material slurry with 42% of solid content; fixing the electrostatic spinning fiber layer prepared in the operation (1) on the surface of a PET substrate, and coating the negative electrode material slurry on the surface of the electrostatic spinning fiber layer in a doctor blade coating mode, wherein the coating thickness is 20 mu m; and after the coating is finished, drying the mixture in a vacuum oven at 100 ℃ for 12 hours, cooling the mixture, and removing the cooled mixture from the surface of the PET substrate to obtain the negative electrode material-fiber composite sheet, wherein the thickness of the negative electrode material-fiber composite sheet is 15 mu m.
(3) Preparing a negative electrode sheet:
and (3) taking a lithium metal-current collector composite sheet formed by compounding a copper foil and lithium metal (the thickness of a lithium layer is 30 microns, the thickness of a copper foil is 10 microns), arranging the negative electrode material-fiber composite sheet and the lithium metal surface of the lithium metal-current collector composite sheet oppositely, and then placing the negative electrode material-fiber composite sheet between pressing plates (10 cm multiplied by 10 cm) of a flat plate hot press, and maintaining the pressure for 5min under 100Mpa to obtain the negative electrode sheet.
In the negative plate prepared in this comparative example, no metal particles were supported in the fiber layer.
Experimental example
Batteries were prepared using the negative electrode sheets of examples 1 to 8 and comparative examples 1 to 4, respectively, as follows:
punching the negative plate and the sulfide electrolyte membrane into a wafer with the diameter of 10mm in an argon glove box; the positive electrode (active material is NCM 811) wafer with the diameter of 10mm which is punched in advance is placed in a mold sleeve, then the sulfide electrolyte membrane wafer and the negative electrode wafer are sequentially placed, and the mold is pressurized by 60Mpa, so that the solid-state battery is obtained.
And (3) carrying out cycle performance test on each solid battery obtained by assembly, wherein the test conditions are as follows: the temperature is 30 ℃, the charge-discharge multiplying power is 0.3 ℃, and the voltage range is 2.5-4.25V (Li) + /Li). The test results are shown in Table 1.
Table 1 results of cycle performance test of each solid-state battery
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (20)
1. The negative electrode plate is characterized by comprising a current collector, and a lithium metal layer and a composite silicon negative electrode layer which are sequentially laminated on at least one surface of the current collector, wherein the composite silicon negative electrode layer is composed of a negative electrode material and a fiber layer embedded in the negative electrode material, the negative electrode material comprises a silicon-based negative electrode material, and metal particles are loaded in the fiber layer;
the fiber layer comprises an electrospun fiber layer comprising electrospun fibers, and the metal particles are loaded in the electrospun fibers.
2. The negative electrode sheet according to claim 1, wherein the thickness of the lithium metal layer is 20 to 80 μm, the thickness of the composite silicon negative electrode layer is 10 to 50 μm, and the thickness of the fiber layer in the composite silicon negative electrode layer is 5 to 20 μm.
3. The negative electrode sheet according to claim 1, wherein the ratio of the thickness of the lithium metal layer to the composite silicon negative electrode layer is (1-3): (1-2).
4. The negative electrode sheet according to claim 1, wherein the weight ratio of the lithium metal layer to the composite silicon negative electrode layer is (1-5): (1-2).
5. The negative electrode sheet according to claim 1, wherein the silicon-based negative electrode material is contained in an amount of 90 to 99wt% based on the total weight of the negative electrode material.
6. The negative electrode sheet according to claim 1, wherein the negative electrode material further comprises a conductive agent and a binder, the conductive agent being 0.5 to 5wt% and the binder being 0.5 to 5wt% based on the total weight of the negative electrode material.
7. The negative electrode sheet according to claim 6, wherein the silicon-based negative electrode material is at least one selected from the group consisting of silicon powder, silicon oxide, silicon thin film, silicon nanowire, silicon nanotube, porous silicon, and hollow structure silicon; the conductive agent is at least one selected from carbon nanotubes, acetylene black, carbon fibers, ketjen black and conductive carbon black; the binder is at least one selected from polyacrylic acid, polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and sodium alginate.
8. The negative electrode sheet according to claim 1, wherein the diameter of the electrospun fiber is 3 to 10 μm and the particle size of the metal particles is 50 to 200nm.
9. The negative electrode sheet according to claim 1, wherein the electrospun fiber is prepared from a polymer raw material selected from at least one of polyethylene oxide, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polyvinylidene fluoride, polycaprolactone, and polymethyl methacrylate.
10. The negative electrode sheet according to claim 1, wherein the metal particles are selected from at least one of silver, gold, copper, aluminum, indium, germanium, sodium, magnesium, chromium, titanium, barium, nickel, molybdenum, cobalt, platinum, zinc, iron, tin, bismuth, and antimony.
11. The negative electrode sheet according to claim 9, wherein the ratio by weight of the polymer raw material to the metal particles in the electrospun fiber is (2 to 5): 1.
12. A method for producing the negative electrode sheet according to any one of claims 1 to 11, characterized by comprising the operations of:
coating the anode material slurry on one surface of a fiber layer, and drying to obtain an anode material-fiber composite sheet; the negative electrode material slurry contains a silicon-based negative electrode material, the negative electrode material-fiber composite sheet consists of a negative electrode material and a fiber layer embedded in the negative electrode material, and metal particles are loaded in the fiber layer;
arranging the negative electrode material-fiber composite sheet and a lithium metal surface of the lithium metal-current collector composite sheet oppositely, and pressing;
the fiber layer is an electrostatic spinning fiber layer, the electrostatic spinning fiber layer comprises electrostatic spinning fibers, and the metal particles are loaded in the electrostatic spinning fibers.
13. The method of claim 12, wherein the process of preparing the electrospun fibrous layer comprises:
taking a polymer raw material, and dissolving the polymer raw material in a solvent to obtain a polymer solution;
adding the metal particles into the polymer solution, and uniformly dispersing to obtain a composite fluid;
and taking the composite fluid, carrying out electrostatic spinning treatment and drying.
14. The method of claim 13, wherein the solvent is selected from at least one of N, N-dimethylformamide, deionized water, tetrahydrofuran, acetone, and N, N-dimethylacetamide.
15. The method of claim 13, wherein the concentration of the polymer feedstock in the polymer solution is from 0.1 to 0.2g/mL.
16. The method of claim 13, wherein the conditions of the electrospinning process comprise: the flow rate of the composite fluid is 0.009-0.02 mL/min, the voltage is 10-20 Kv, the collecting distance is 10-15 cm, the temperature is 20-30 ℃ and the time is 1-3 h.
17. The method of claim 12, wherein the lithium metal-current collector composite sheet consists of a current collector and lithium metal on one surface of the current collector.
18. The method of claim 12, wherein the pressure of the press-fit is 50-200 Mpa for 3-10 min.
19. A battery comprising the negative electrode sheet according to any one of claims 1 to 11.
20. The battery according to claim 19, wherein the battery is any one of a liquid-phase lithium secondary battery, a semi-solid-state lithium secondary battery, and an all-solid-state lithium secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211009709.9A CN115188919B (en) | 2022-08-22 | 2022-08-22 | Negative plate, preparation method thereof and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211009709.9A CN115188919B (en) | 2022-08-22 | 2022-08-22 | Negative plate, preparation method thereof and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115188919A CN115188919A (en) | 2022-10-14 |
| CN115188919B true CN115188919B (en) | 2024-01-02 |
Family
ID=83523209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211009709.9A Active CN115188919B (en) | 2022-08-22 | 2022-08-22 | Negative plate, preparation method thereof and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115188919B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112216811A (en) * | 2020-09-23 | 2021-01-12 | 电子科技大学 | Preparation method of ultrathin lithium metal cathode |
| CN113584723A (en) * | 2021-08-02 | 2021-11-02 | 岭南师范学院 | Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof |
| CN113725400A (en) * | 2021-08-25 | 2021-11-30 | 远景动力技术(江苏)有限公司 | Pre-lithiated silicon-carbon negative plate and preparation method and application thereof |
| CN113921901A (en) * | 2021-11-18 | 2022-01-11 | 北京化工大学 | Metal organic framework based composite nanofiber membrane and preparation method and application thereof |
| CN114256462A (en) * | 2021-11-24 | 2022-03-29 | 郑州大学 | Preparation method of lithium battery negative electrode material |
| CN114824171A (en) * | 2022-05-05 | 2022-07-29 | 浙江锋锂新能源科技有限公司 | Preparation method of multilayer battery pole piece and multilayer battery pole piece |
-
2022
- 2022-08-22 CN CN202211009709.9A patent/CN115188919B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112216811A (en) * | 2020-09-23 | 2021-01-12 | 电子科技大学 | Preparation method of ultrathin lithium metal cathode |
| CN113584723A (en) * | 2021-08-02 | 2021-11-02 | 岭南师范学院 | Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof |
| CN113725400A (en) * | 2021-08-25 | 2021-11-30 | 远景动力技术(江苏)有限公司 | Pre-lithiated silicon-carbon negative plate and preparation method and application thereof |
| CN113921901A (en) * | 2021-11-18 | 2022-01-11 | 北京化工大学 | Metal organic framework based composite nanofiber membrane and preparation method and application thereof |
| CN114256462A (en) * | 2021-11-24 | 2022-03-29 | 郑州大学 | Preparation method of lithium battery negative electrode material |
| CN114824171A (en) * | 2022-05-05 | 2022-07-29 | 浙江锋锂新能源科技有限公司 | Preparation method of multilayer battery pole piece and multilayer battery pole piece |
Non-Patent Citations (1)
| Title |
|---|
| 锂金属负极中抑制锂枝晶生长的研究进展;陈涛等;电池工业;第25卷(第4期);216-220 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115188919A (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112038574B (en) | Pole piece film and preparation method and application thereof | |
| CN109256555B (en) | Chalcogenide composite positive electrode material, all-solid-state lithium battery and preparation methods thereof | |
| CN107394261B (en) | Inorganic/organic composite film solid electrolyte for lithium metal battery and preparation method thereof | |
| CN110739485A (en) | low-temperature lithium ion batteries | |
| CN105098138B (en) | Negative electrode for lithium ion battery piece and preparation method thereof | |
| CN107248569B (en) | Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof | |
| CN112886011A (en) | Composite lithium supplementing film and preparation method and application thereof | |
| CN106784741B (en) | Carbon-silicon composite material, preparation method thereof and lithium ion battery containing composite material | |
| CN108963265B (en) | Negative current collector for lithium metal battery and preparation method thereof | |
| CN113659104A (en) | Preparation method of battery active layer, battery pole piece and application | |
| CN112467200B (en) | Lithium fluoride/lithium lanthanum titanate nanofiber solid electrolyte interface material and preparation method and application thereof | |
| CN113851609A (en) | Silicon-based negative electrode plate, preparation method thereof and all-solid-state lithium ion battery | |
| CN113851648A (en) | Composite negative electrode for solid-state battery, preparation method of composite negative electrode and solid-state battery | |
| WO2023123752A1 (en) | Polar current collector and preparation method therefor | |
| CN112786869B (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
| CN113363421A (en) | Lithium metal negative electrode layer and preparation method and application thereof | |
| CN113571681A (en) | Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof | |
| CN111705315B (en) | Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery | |
| CN115188919B (en) | Negative plate, preparation method thereof and battery | |
| CN116376280A (en) | Poly (p-phenylene benzobisoxazole) porous membrane, preparation method and application thereof, composite membrane and battery | |
| CN114678490A (en) | Lithium ion battery negative plate and preparation method thereof | |
| CN112397701A (en) | Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof | |
| CN111933866A (en) | Lithium metal battery, interlayer thereof and preparation method | |
| CN110752357A (en) | Porous Fe-based amorphous alloy coated silicon cathode of lithium battery and preparation method | |
| CN115513444B (en) | Silicon @ carbon-graphite composite anode material, composite layer anode piece and secondary battery thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |