CN114843439A - Composite magnesium-lithium alloy negative plate and preparation method and application thereof - Google Patents
Composite magnesium-lithium alloy negative plate and preparation method and application thereof Download PDFInfo
- Publication number
- CN114843439A CN114843439A CN202210703959.6A CN202210703959A CN114843439A CN 114843439 A CN114843439 A CN 114843439A CN 202210703959 A CN202210703959 A CN 202210703959A CN 114843439 A CN114843439 A CN 114843439A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- lithium alloy
- lithium
- silicon
- active material
- 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.)
- Pending
Links
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910000733 Li alloy Inorganic materials 0.000 title claims abstract description 92
- 239000001989 lithium alloy Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000440 bentonite Substances 0.000 claims abstract description 35
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 35
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 47
- 239000002409 silicon-based active material Substances 0.000 claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 239000011247 coating layer Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 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 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 12
- 239000002210 silicon-based material Substances 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 235000012216 bentonite Nutrition 0.000 description 26
- 230000002829 reductive effect Effects 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910000861 Mg alloy Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011856 silicon-based particle Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910005321 Li15Si4 Inorganic materials 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002900 effect on cell Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
The invention discloses a composite magnesium-lithium alloy negative plate and a preparation method and application thereof, belonging to the field of lithium ion batteries. This compound magnesium lithium alloy negative pole piece, including magnesium lithium alloy current collection layer and coat in the bentonite mixture adhesive and the silica-based active material mixed dope layer on magnesium lithium alloy current collection layer, bentonite mixture adhesive has alkali metal oxide structure, can reduce magnesium lithium alloy corrosion current, make the characteristics that the corrosion potential moved forward, and simultaneously, along with silica-based active material inflation, the good expansion capacity of bentonite makes silicon be difficult for with the mass flow body separation, the structural integrity of negative pole end has been guaranteed, the coulomb efficiency of battery has been improved. Meanwhile, due to the good expansion capacity of the bentonite, the electronic channel failure of the current collector caused by the volume expansion of the silicon-based material is avoided.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite magnesium-lithium alloy negative plate and a preparation method and application thereof.
Background
With the use of lithium ion batteries as power batteries, electric vehicles have been developed dramatically, but negative electrode sheets made of graphite and copper foil have failed to meet the requirements of lithium ion batteries for high specific energy, high power output, etc., and therefore, how to improve the rate capability and energy density of lithium batteries has been the subject of research by the present inventors.
Lithium metal is the most ideal negative plate of a lithium battery due to the advantage of high specific energy, but when the lithium metal is used as a negative electrode material of the lithium ion battery, the problems that lithium ion flux is not uniform, current density is high, lithium dendrite is easy to generate, the activity of lithium ion self-generated metal can cause infinite volume change and the like exist, and the safety and the rate performance of the battery can be irreversibly influenced.
The lithium magnesium alloy has the characteristics of being super-light, easy to shape, strong in shock absorption performance and the like as the magnesium alloy with the minimum density. When the magnesium-lithium alloy is used as a lithium ion battery cathode material, the magnesium skeleton in the magnesium-lithium alloy ensures the stability of the cathode active material, and is not easy to break, pulverize, bulge and dendrite in the circulation process. Meanwhile, the lithium magnesium alloy has high and stable lithium deposition/dissolution efficiency, is easier to form a stable solid electrolyte interface film (SEI film), and reduces the occurrence of side reactions. However, when a magnesium-lithium alloy is used for the negative electrode terminal material of a commercial battery cell, the following problems still remain: (1) in the electrolyte, the corrosion current of the magnesium-lithium alloy is increased due to the negative difference effect, and magnesium ions are gradually dissolved out; (2) a layer of gray film is easily generated on the surface of the magnesium-lithium alloy, so that lithium ions cannot penetrate through the gray film, and the electrochemical performance is influenced; (3) after the magnesium-lithium alloy is corroded, polarization resistance is increased, current density is reduced, and rate performance is affected.
Another common cathode high specific energy material is silicon material (high temperature 4200mAh/g, room temperature 3580mAh/g), which has the advantages of low delithiation potential (< 0.5V), environmental friendliness, abundant reserves, low cost and the like, thus being considered as a cathode material of a lithium ion battery with great potential. However, there are still two key problems to be solved in the commercial mass production of silicon-based anode materials: (1) the volume change (more than or equal to 300%) of the repeated expansion and contraction of the silicon material in the lithium extraction process is easy to pulverize and fall off, and finally the active material loses electric contact to completely disable the battery; (2) the continuous growth of the SEI film on the surface of the silicon material irreversibly consumes the limited electrolyte in the battery and lithium from the positive electrode all the time, eventually leading to rapid degradation of the battery capacity.
Disclosure of Invention
1. Problems to be solved
In order to solve one of the problems that the silicon material is easy to be pulverized and fall off in the process of lithium intercalation and deintercalation, the invention provides a composite magnesium-lithium alloy negative plate which comprises a magnesium-lithium alloy current collecting layer and a silicon-based active material mixed coating layer coated on at least one surface of the magnesium-lithium alloy current collecting layer, wherein the silicon-based active material mixed coating comprises a bentonite mixture adhesive and a silicon-based active material; on the other hand, as the silicon-based active material expands, the silicon is not easy to separate from the current collector due to the good expansion capacity of the bentonite, the structural integrity of the cathode end is ensured, and the coulomb efficiency of the battery is improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a composite magnesium-lithium alloy negative plate, which comprises a magnesium-lithium alloy current collecting layer and a silicon-based active material mixed coating layer coated on the surface of the magnesium-lithium alloy current collecting layer, wherein the silicon-based active material mixed coating comprises a bentonite mixture adhesive and a silicon-based active material; on the other hand, as the silicon-based active material expands, the silicon is not easy to separate from the current collector due to the good expansion capacity of the bentonite, the structural integrity of the cathode end is ensured, and the coulomb efficiency of the battery is improved.
Preferably, both surfaces of the magnesium-lithium alloy current collecting layer are coated with silicon-based active material mixed coating layers.
Preferably, the coating refers to a battery coating process, i.e., a process of uniformly coating a slurry with good stability, viscosity and fluidity on a current collector, including transfer coating and extrusion coating.
Preferably, the bentonite mixture adhesive contains 0.5-10% of bentonite by mass. Furthermore, the content of the bentonite is 0.5 to 5 percent. Further, the bentonite content was 0.5%, 1%, 1.5%, 2%, 3%, 4% and 5%. The bentonite has a structure that an X oxygen tetrahedral sheet sandwiches a Y oxygen octahedral sheet, wherein X and Y can be one or more of aluminum, silicon, calcium, magnesium, sodium or potassium, and the alkali metal oxide structure can form a layer of passivation film on the surface of the magnesium-lithium alloy, reduce the corrosion current of the lithium-magnesium alloy and effectively prevent the current collector structure from being broken due to magnesium ion dissolution; and when the magnesium-lithium alloy is protected by the bentonite, the bentonite has excellent expansion tolerance and high dispersibility, so that the bentonite has an inhibiting effect on electric contact disappearance caused by silicon expansion and contraction, and the cycle stability and the coulombic efficiency of the negative plate are improved.
Preferably, a polypropylene-based polymer is used in the bentonite mixture binder. The polypropylene contains carboxyl functional groups with higher concentration, and abundant carboxyl and silicon particles form a large number of chemical bonds, so that the stability of the electrode material is improved; the polypropylene polymer also has a 3D structure, so that the mixture binder and the silicon surface form multi-point interaction, the silicon particles are effectively prevented from being separated, and the cycling stability of the battery is further improved. In addition, the 3D structure is established while the mechanical and electrochemical properties of the binder are improved by adding components with high elasticity and high conductivity and inhibiting the decomposition of electrolyte, so that the stability is satisfied while the capacity characteristic is increased.
Preferably, the polypropylene polymer comprises one or more of polyacrylic acid, polyacrylic acid-carboxymethyl cellulose, polyacrylic acid-polyethyleneimine, polyamic acid-polyacrylic acid or polyester-polyacrylic acid.
Preferably, the silicon-based active material includes one or more of nano-silicon, silicon oxide, silicon monoxide, carbon composite silicon oxide, carbon composite silicon monoxide and other silicon-containing materials. The silicon material has higher specific energy (Li22Si5:4200 mAh/g; Li15Si4:35700mAh/g), and the selection of the proper composite silicon material as the active material is beneficial to improving the first efficiency, the cycle performance and the battery safety.
Preferably, the thickness of the silicon-based active material mixed coating layer is 10 to 50 μm. Further, the thickness of the silicon-based active material layer is 10 μm to 30 μm. Further, the thickness of the silicon-based active material layer is 10 μm to 15 μm.
Preferably, the lithium content of the magnesium-lithium alloy current collector layer is 2 to 30%. Furthermore, the lithium content of the magnesium-lithium alloy current collecting layer is 5-10%. Further, the lithium content of the magnesium-lithium alloy current collector layer is preferably 5% to 8%. In the magnesium-lithium alloy, the content (atomic ratio) of lithium is in a proper range, so that the plasticity of the magnesium-lithium alloy can be improved, the density of the magnesium-lithium alloy can be reduced, and the stability of a foil can be ensured; the current collector can enable the battery to have lower volume and weight, and improve the conductivity of the battery, thereby improving the energy density and the power density; when the lithium content is between 5% and 10%, the alloy is a two-phase structure of a close-packed hexagonal structure alpha + a body-centered cubic structure beta, and the body-centered cubic lattice has a slip system, so that the processing of a pole piece is facilitated; when the lithium content is 5-8%, the corrosion resistance of the alloy is optimal, and the cycling performance of the pole piece can be improved and failure can be prevented when the alloy is contacted with electrolyte for a long time.
Preferably, the magnesium-lithium alloy current collecting layer also comprises other elements, such as one or more of aluminum, zinc, manganese and silver, and the content of the elements is less than or equal to 5%. Due to the objective fact that the magnesium-lithium alloy has a negative difference effect, part of elements added during the selection of the magnesium-lithium alloy can improve the performance of the magnesium-lithium alloy in all aspects, for example, aluminum can improve the hydrogen evolution potential of the alloy, so that a passivation film is formed on the surface of the alloy, and the energy storage performance is improved; when the aluminum is added, the zinc is added, so that the segregation of the aluminum in magnesium-lithium crystal boundaries can be reduced, and the cavitation erosion is prevented; the addition of manganese can refine crystal grains and play a certain role in solid solution strengthening, so that the open circuit potential of the battery is increased, but the anode efficiency is relatively reduced.
Preferably, the thickness of the magnesium-lithium alloy current collector layer is 5 to 20 μm. Further, the thickness of the magnesium-lithium alloy current collecting layer is 5 to 10 μm.
Preferably, the magnesium-lithium alloy current collector layer has a tensile strength of 200-450 MP. Furthermore, the tensile strength of the magnesium-lithium alloy current collecting layer is 300-400 MP. As a current collector layer, the magnesium-lithium alloy needs to have higher mechanical property, plays a stable supporting role for a negative active material, ensures the structural integrity of the negative active material, prevents a pole piece from being fractured, pulverized, folded and the like, and can effectively prevent the active material from being separated to cause the failure of the battery when the battery is subjected to larger deformation.
Preferably, the magnesium-lithium alloy current collector layer has an elongation of 3% to 15%. Further, the magnesium-lithium alloy has an elongation of 8% to 15%. Further, the elongation of the magnesium-lithium alloy is 8%, 9%, 10%, 11%, 12%, 13%, and 14%. When the magnesium-lithium alloy is used as a current collecting layer, the magnesium-lithium alloy needs to have sufficient elongation to prevent the foil from generating internal stress in the rolling process, so that the splitting occurs to influence the capacity and safety of the battery and the like.
Preferably, the peel strength between the silicon-based active material mixed coating layer (bentonite mixture adhesive/silicon-based active material) and the magnesium-lithium alloy current collecting layer in the composite negative plate is more than or equal to 30mN/mm before rolling and more than or equal to 15mN/mm after rolling. The peel strength between the active material layer and the magnesium-lithium alloy layer is high, so that the active material is not easy to remove a current collecting layer in the charging and discharging process, and the improvement of the battery cyclicity is facilitated.
Preferably, the puncture resistance strength of the composite negative plate is more than or equal to 1 kN/mm. Further, the puncture resistance strength of the negative electrode sheet is 3kN/mm to 10 kN/mm. Furthermore, the puncture resistance strength of the negative electrode piece is 3kN/mm, 4kN/mm, 5kN/mm, 6kN/mm, 7kN/mm, 8kN/mm, 9kN/mm or 10 kN/mm. The puncture resistance of the negative plate improves the nail penetration safety of the lithium battery; the puncture resistance strength also reflects the flexibility of the pole piece, and is beneficial to reducing the fracture of the pole piece in the rolling and winding processes.
Preferably, the tensile strength of the composite negative electrode sheet is 230MP to 480 MP. Further, the tensile strength of the negative electrode sheet is 330MP to 430 MP. The negative pole piece also needs higher mechanical strength, so that the pole piece is effectively prevented from being broken off, and the battery is ensured to have higher cycle performance.
The invention provides a preparation method of the composite magnesium-lithium alloy negative plate, which comprises the steps of mixing polyacrylic acid polymer, bentonite and silicon-based active materials, dissolving the mixture in deionized water to form mixed slurry, and uniformly coating the mixed slurry on the surface of a magnesium-lithium alloy current collecting layer.
Preferably, the mass ratio of the silicon-based active material in the mixed slurry is 90-98%. Furthermore, the mass ratio of the silicon-based active material in the mixed slurry is 93-96%.
The invention also provides application of the composite magnesium-lithium alloy negative plate as a lithium ion battery negative plate.
The invention also provides an application of the preparation method of the composite magnesium-lithium alloy negative plate in the preparation of a lithium ion battery.
The invention also provides a lithium ion battery which comprises a positive plate, a negative plate and electrolyte, wherein the negative plate is the composite magnesium-lithium alloy negative plate.
Preferably, the positive electrode sheet includes a positive electrode current collector layer, and the positive electrode active material layer disposed on at least one surface of the positive electrode current collector layer is not limited to one or more of lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, manganese nickel cobalt composite oxide, lithium vanadium oxide, or lithium iron oxide.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a composite magnesium-lithium alloy negative plate which comprises a magnesium-lithium alloy current collecting layer, and a bentonite mixture adhesive and a silicon-based active material mixed coating which are coated on the magnesium-lithium alloy current collecting layer, wherein the bentonite mixture adhesive has an alkali metal oxide structure and can reduce corrosion current of magnesium-lithium alloy and enable corrosion potential to move forward. Meanwhile, as the silicon-based active material expands, the silicon is not easy to separate from the current collector due to the good expansion capacity of the bentonite, the structural integrity of the cathode end is ensured, and the coulomb efficiency of the battery is improved.
(2) According to the composite magnesium-lithium alloy negative plate provided by the invention, the bentonite mixture adhesive can be simultaneously used as a passivation film on the surface of the magnesium-lithium alloy, and a structural framework capable of preventing the loss of an active material caused by silicon expansion can be prevented.
Drawings
Fig. 1 is an explanatory view of an embodiment of a negative electrode sheet, in which reference numeral 1 is an upper silicon-based active material mixed coating layer (bentonite mixture binder and silicon-based active material), reference numeral 2 is a magnesium-lithium alloy current collecting layer, and reference numeral 3 is a lower silicon-based active material mixed coating layer (bentonite mixture binder and silicon-based active material).
Detailed Description
The invention is further described with reference to specific examples.
It should be noted that the terms "upper", "lower", "left", "right" and "middle" used in the present specification are for the sake of clarity, and are not intended to limit the scope of the present invention, and changes or adjustments of the relative relationship thereof may be made without substantial technical changes.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, measure or value. The degree of flexibility for a particular variable can be readily determined by one skilled in the art.
As used herein, at least one of the terms "is intended to be synonymous with one or more of. For example, "at least one of A, B and C" explicitly includes a only, B only, C only, and combinations thereof, respectively.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limit values of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all of the aforementioned values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or feature being described.
Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims.
Examples
Fig. 1 is a structural explanatory view of an embodiment of the composite magnesium-lithium alloy negative electrode sheet of the present invention, in which reference numeral 1 is an upper silicon-based active material mixed coating layer (bentonite mixture binder and silicon-based active material), reference numeral 2 is a magnesium-lithium alloy current collector layer, and reference numeral 3 is a lower silicon-based active material mixed coating layer (bentonite mixture binder and silicon-based active material).
The composition and the cell test result of the composite magnesium-lithium alloy negative plate provided by the invention are shown in table 1.
Table 1 composition of composite magnesium-lithium alloy negative electrode sheet and cell test results provided by the present invention
From the experimental data of examples 1-5, the thickness of the magnesium-lithium alloy foil can affect the first effect and the cycle performance of the battery cell. In the first charge and discharge process, when the silicon material captures lithium ions to generate a certain amount of irreversible lithium, the magnesium-lithium alloy provides sufficient lithium ions, so that the first effect of the battery is ensured. But the elongation of the pole piece is also reduced due to the increased thickness of the current collector, so that the cycle performance of the corresponding lithium battery is reduced.
From the experimental data of examples 6-12, the effect of different lithium content magnesium lithium alloy foils on the cell is known. When the lithium content is too low, the tensile strength of the foil is reduced and the conductivity is reduced. When the lithium content exceeds 10%, lithium dendrites are easily generated, thereby generating dead lithium, which affects the cycle performance of the battery.
The effect of the content of different bentonites in the mixed binder on the cell performance can be seen from the experimental data of examples 13-18. When the content of the bentonite is 0.5-5%, the peel strength of the negative pole piece before rolling can be greater than 40mN/mm, and the high peel strength ensures that the risk that an active material is separated from a current collector is not easy to generate in the charge and discharge process of the pole piece, so that the cycle performance of the battery cell is enhanced.
From the experimental data of examples 19-24, it can be seen that different silicon material contents have an effect on cell performance. The increase of the silicon material can lead to the increase of the expansion of the negative plate, the damage reconstruction of an SEI film can be caused, an electric island and the like are generated, lithium ions can be continuously consumed by a series of reactions, and the first effect of the electric core is reduced.
From the experimental data of comparative examples 1-3, it can be seen that the cell performance was not affected by the presence of the bentonite binder. During the cycle, the silicon-based material gradually expands, creating the risk of detachment from the current collector. In addition, in the circulation process of the magnesium-lithium alloy, because the magnesium-lithium alloy has self-corrosiveness, magnesium ions are separated out, the structural integrity of a current collector is reduced, and the circulation performance of a battery cell is reduced.
In the present application, the example negative electrode sheets are all parameters in which the active material layers are disposed on both sides. When the active material described herein is coated on both surfaces of the lithium magnesium alloy, the active material on either surface satisfies the present application, which is considered to fall within the scope of the present application.
Claims (16)
1. The composite magnesium-lithium alloy negative plate is characterized by comprising a magnesium-lithium alloy current collecting layer and a silicon-based active material mixed coating layer coated on at least one surface of the magnesium-lithium alloy current collecting layer, wherein the silicon-based active material mixed coating comprises a bentonite mixture adhesive and a silicon-based active material.
2. The composite magnesium-lithium alloy negative plate as claimed in claim 1, wherein the upper surface and the lower surface of the magnesium-lithium alloy current collecting layer are coated with right silicon-based active material mixed coating layers.
3. The composite magnesium-lithium alloy negative plate according to claim 1 or 2, wherein the thickness of the magnesium-lithium alloy current collecting layer is 5 μm to 20 μm, and/or the thickness of the silicon-based active material mixed coating layer is 10 μm to 50 μm.
4. The negative electrode sheet of claim 3, wherein the bentonite mixture binder comprises bentonite and polypropylene polymer, and the bentonite accounts for 0.5-10% by mass.
5. The composite magnesium-lithium alloy negative electrode sheet according to claim 4, wherein the bentonite has a structure of X oxygen tetrahedral sheet sandwiched by Y oxygen octahedral sheet, wherein X and Y can be one or more of aluminum, silicon, calcium, magnesium, sodium or potassium.
6. The composite magnesium-lithium alloy negative electrode sheet according to claim 4 or 5, wherein the polypropylene polymer comprises one or more of polyacrylic acid, polyacrylic acid-carboxymethyl cellulose, polyacrylic acid-polyethyleneimine, polyamic acid-polyacrylic acid or polyester-polyacrylic acid.
7. The composite magnesium-lithium alloy negative electrode plate according to claim 6, wherein the silicon-based active material comprises one or more of nano-silicon, silicon oxide, silicon monoxide, carbon composite silicon oxide or carbon composite silicon monoxide.
8. The composite magnesium lithium alloy negative plate according to claim 7, wherein the lithium content of the magnesium lithium alloy current collecting layer is 2-30%; and/or the tensile strength of the magnesium-lithium alloy current collecting layer is 200 MP-450 MP; and/or the elongation of the magnesium-lithium alloy current collecting layer is 3-15%.
9. The composite magnesium-lithium alloy negative electrode sheet according to claim 8, wherein the magnesium-lithium alloy current collecting layer further comprises one or more of aluminum, zinc, manganese and silver, and the content of the one or more of aluminum, zinc, manganese and silver is less than or equal to 5%.
10. The composite magnesium-lithium alloy negative plate according to claim 7 or 8, wherein the peel strength between the silicon-based active material mixed coating layer and the magnesium-lithium alloy current collecting layer is more than or equal to 30mN/mm before rolling and more than or equal to 15mN/mm after rolling; and/or the puncture resistance strength of the composite magnesium-lithium alloy negative plate is more than or equal to 1 kN/mm; and/or the tensile strength of the composite magnesium-lithium alloy negative plate is 230-480 MP.
11. The method for preparing the composite magnesium-lithium alloy negative plate as claimed in any one of claims 1 to 10, wherein the polyacrylic acid polymer, the bentonite and the silicon-based active material are mixed and dissolved in deionized water to form a mixed slurry, and the mixed slurry is uniformly coated on the surface of the magnesium-lithium alloy current collecting layer.
12. The method for preparing the composite magnesium-lithium alloy negative plate according to claim 11, wherein the mass proportion of the silicon-based active material in the mixed slurry is 90-98%.
13. Use of a negative electrode sheet of a composite magnesium lithium alloy according to any one of claims 1 to 10 and/or a negative electrode sheet of a composite magnesium lithium alloy according to any one of claims 11 to 12 in the preparation of a lithium ion battery.
14. A lithium ion battery, characterized in that, it comprises a positive plate, a negative plate and electrolyte, the negative plate is a composite magnesium-lithium alloy negative plate according to any one of claims 1 to 10.
15. The lithium ion battery of claim 14, wherein the positive plate comprises a positive current collector layer, and a positive active material layer disposed on at least one side of the positive current collector layer.
16. The lithium ion battery of claim 15, wherein the positive electrode active layer comprises one or more of lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, manganese nickel cobalt composite oxide, lithium vanadium oxide, or lithium iron oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210703959.6A CN114843439A (en) | 2022-06-21 | 2022-06-21 | Composite magnesium-lithium alloy negative plate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210703959.6A CN114843439A (en) | 2022-06-21 | 2022-06-21 | Composite magnesium-lithium alloy negative plate and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114843439A true CN114843439A (en) | 2022-08-02 |
Family
ID=82574421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210703959.6A Pending CN114843439A (en) | 2022-06-21 | 2022-06-21 | Composite magnesium-lithium alloy negative plate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114843439A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002042889A (en) * | 2000-07-21 | 2002-02-08 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| JP2007242405A (en) * | 2006-03-08 | 2007-09-20 | Sanyo Electric Co Ltd | Negative electrode for lithium secondary battery and its manufacturing method, as well as lithium secondary battery |
| JP2011144440A (en) * | 2010-01-18 | 2011-07-28 | Sumitomo Light Metal Ind Ltd | Aluminum alloy foil for lithium ion battery electrode current collector |
| CN104313386A (en) * | 2014-09-24 | 2015-01-28 | 襄阳锦翔光电科技股份有限公司 | Copper alloy for negative current collector of lithium ion battery |
| US20180034047A1 (en) * | 2016-07-28 | 2018-02-01 | Samsung Sdi Co., Ltd. | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
| CN110098379A (en) * | 2019-04-25 | 2019-08-06 | 浙江锋锂新能源科技有限公司 | A kind of lithium an- ode and preparation method thereof and lithium battery using the cathode |
| CN110556532A (en) * | 2018-06-01 | 2019-12-10 | 中能中科（天津）新能源科技有限公司 | reticular lithium material and preparation method and application thereof |
| CN107615550B (en) * | 2016-05-06 | 2020-10-27 | 深圳中科瑞能实业有限公司 | Secondary battery and preparation method thereof |
| KR20210097484A (en) * | 2020-01-30 | 2021-08-09 | 울산과학기술원 | Anode active material for rechargeable lithium battery and manufacturing method thereof |
| CN113488656A (en) * | 2020-08-31 | 2021-10-08 | 中南大学 | 3D lithium-philic composite porous metal alloy current collector and preparation method and application thereof |
| CN114258603A (en) * | 2021-03-31 | 2022-03-29 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
-
2022
- 2022-06-21 CN CN202210703959.6A patent/CN114843439A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002042889A (en) * | 2000-07-21 | 2002-02-08 | Toshiba Corp | Nonaqueous electrolyte secondary battery |
| JP2007242405A (en) * | 2006-03-08 | 2007-09-20 | Sanyo Electric Co Ltd | Negative electrode for lithium secondary battery and its manufacturing method, as well as lithium secondary battery |
| JP2011144440A (en) * | 2010-01-18 | 2011-07-28 | Sumitomo Light Metal Ind Ltd | Aluminum alloy foil for lithium ion battery electrode current collector |
| CN104313386A (en) * | 2014-09-24 | 2015-01-28 | 襄阳锦翔光电科技股份有限公司 | Copper alloy for negative current collector of lithium ion battery |
| CN107615550B (en) * | 2016-05-06 | 2020-10-27 | 深圳中科瑞能实业有限公司 | Secondary battery and preparation method thereof |
| US20180034047A1 (en) * | 2016-07-28 | 2018-02-01 | Samsung Sdi Co., Ltd. | Negative electrode for rechargeable lithium battery, and rechargeable lithium battery including same |
| CN110556532A (en) * | 2018-06-01 | 2019-12-10 | 中能中科（天津）新能源科技有限公司 | reticular lithium material and preparation method and application thereof |
| CN110098379A (en) * | 2019-04-25 | 2019-08-06 | 浙江锋锂新能源科技有限公司 | A kind of lithium an- ode and preparation method thereof and lithium battery using the cathode |
| KR20210097484A (en) * | 2020-01-30 | 2021-08-09 | 울산과학기술원 | Anode active material for rechargeable lithium battery and manufacturing method thereof |
| CN113488656A (en) * | 2020-08-31 | 2021-10-08 | 中南大学 | 3D lithium-philic composite porous metal alloy current collector and preparation method and application thereof |
| CN114258603A (en) * | 2021-03-31 | 2022-03-29 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Non-Patent Citations (1)
| Title |
|---|
| 邓攀等: ""锂离子电池硅基负极黏结剂研究进展"", vol. 8, no. 8, pages 413 - 427 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3451423B1 (en) | Negative electrode slurry, negative electrode plate and electrochemical energy storage device | |
| CN108172761B (en) | Composite negative electrode for lithium secondary battery, and preparation and application thereof | |
| CN103733398B (en) | Collector body, electrode assembly, nonaqueous electrolyte battery and electric power storage parts | |
| EP1903628A2 (en) | A Negative Electrode Active Material for an Electricity Storage Device and Method for Manufacturing the Same | |
| CN102856557B (en) | Novel battery | |
| JP2000215897A (en) | Lithium secondary battery | |
| CN112825354B (en) | Lithium negative electrode, preparation method thereof and lithium secondary battery | |
| EP3819962A1 (en) | Negative electrode layer for all-solid secondary battery, all-solid secondary battery including the same, and preparation method thereof | |
| CN104854735B (en) | Electrical equipment is with anode and uses its electrical equipment | |
| CN110660996B (en) | Electrode plate and electrochemical device | |
| CN113410427A (en) | Positive pole piece and preparation method and application thereof | |
| KR20140051375A (en) | Metal foil with coating layer and method for producing same, secondary cell electrode and method for producing same, and lithium ion secondary cell | |
| EP4362123A1 (en) | Negative electrode sheet and battery applying same | |
| CN112331843A (en) | Positive electrode material, positive electrode, preparation method of positive electrode and lithium secondary battery | |
| CN112103509A (en) | Positive current collector, positive plate, lithium ion battery and battery module | |
| CN104813510B (en) | Negative electrode for electrical device and electrical device provided with same | |
| EP4235847A1 (en) | Lithium ion battery | |
| JP2009199744A (en) | Negative electrode for lithium secondary battery and its manufacturing method | |
| US11069891B2 (en) | Battery, battery pack and continuous power supply | |
| CN108963241B (en) | Battery, battery pack and uninterruptible power supply | |
| CN112490425A (en) | Flexible composite lithium metal electrode, preparation thereof and lithium metal battery | |
| CN114843439A (en) | Composite magnesium-lithium alloy negative plate and preparation method and application thereof | |
| WO2023028983A1 (en) | Metal foil and method for preparing same, and current collector, electrode, battery and electric device | |
| CN112436106B (en) | Metal positive electrode and battery based on metal positive electrode | |
| CN109314226A (en) | Lithium ion secondary battery |
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 |