CN116454543A - Diaphragm, preparation method thereof, energy storage device and electric equipment - Google Patents
Diaphragm, preparation method thereof, energy storage device and electric equipment Download PDFInfo
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- CN116454543A CN116454543A CN202310712653.1A CN202310712653A CN116454543A CN 116454543 A CN116454543 A CN 116454543A CN 202310712653 A CN202310712653 A CN 202310712653A CN 116454543 A CN116454543 A CN 116454543A
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- lithium
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- diaphragm
- core
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- 238000004146 energy storage Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 57
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 30
- 229920000615 alginic acid Polymers 0.000 claims abstract description 30
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229940072056 alginate Drugs 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000005253 cladding Methods 0.000 claims abstract 6
- 230000001502 supplementing effect Effects 0.000 claims description 52
- 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 28
- 239000000661 sodium alginate Substances 0.000 claims description 28
- 235000010413 sodium alginate Nutrition 0.000 claims description 28
- 229940005550 sodium alginate Drugs 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 238000007590 electrostatic spraying Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 20
- 150000003841 chloride salts Chemical class 0.000 claims description 17
- 229910001510 metal chloride Inorganic materials 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000648 calcium alginate Substances 0.000 claims description 10
- 235000010410 calcium alginate Nutrition 0.000 claims description 10
- 229960002681 calcium alginate Drugs 0.000 claims description 10
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 2
- 230000001351 cycling effect Effects 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 5
- 239000008187 granular material Substances 0.000 abstract 3
- 230000003020 moisturizing effect Effects 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses diaphragm and preparation method thereof, energy storage device and consumer, the diaphragm includes basic film and attaches the moisturizing coating on basic film at least one side surface, the moisturizing coating includes a plurality of first granule that have core-shell structure, first granule has a nuclear and the cladding shell layer that is located nuclear surface, cladding shell layer adheres to the surface of nuclear, the nuclear has carbon-coated lithium structure, carbon-coated lithium structure is the layer that contains the carbon element and at least partly coats the second granule that contains the lithium element, cladding shell layer includes the alginate polymer that bonds with the basic film, in secondary battery formation stage and cyclic process, the alginate polymer is configured into and can swell in the electrolyte in order to form a plurality of passageways that the electrolyte soaks to the surface and the inside of nuclear. The diaphragm provided by the application ensures that the diaphragm basic function prevents the positive electrode and the negative electrode from being contacted with each other, and meanwhile, the consumed active lithium can be compensated, so that the energy density, the low-temperature performance, the multiplying power performance and the cycle performance of the battery are improved.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a diaphragm, a preparation method thereof, an energy storage device and electric equipment.
Background
Compared with other types of diaphragms, after the hot pressing process of the lithium battery, the PVDF coating of the glued diaphragm can be thermally fused with the binder in the electrode, so that the mechanical strength of the battery is remarkably improved, deformation in the battery circulation process is prevented, and the circulation performance and the safety performance can be remarkably improved.
Currently, the separator in the related art generally includes: the ceramic diaphragm, the PVDF coating diaphragm or the water-based ceramic and PVDF mixed coating diaphragm and the like, but the coating diaphragm used in the lithium ion battery at present is a chemically inert material, and the exertion of the electrochemical performance of the positive and negative electrode main materials can be influenced to a certain extent, so that the diaphragm which can ensure the basic function of the diaphragm and simultaneously can slowly release and supplement lithium is necessary.
Disclosure of Invention
In view of the foregoing drawbacks or shortcomings in the prior art, it is desirable to provide a separator, a method for manufacturing the same, an energy storage device, and an electric device, wherein the separator can compensate consumed active lithium while ensuring a basic function of the separator to prevent positive and negative electrodes from contacting each other, thereby improving battery performance.
In a first aspect, the present invention provides a separator for a secondary battery comprising an electrolyte, characterized by comprising a base film and a lithium supplementing coating layer attached to at least one side surface of the base film, the lithium supplementing coating layer comprising a plurality of first particles having a core-shell structure, the first particles having a core and a coating shell layer on the surface of the core, the coating shell layer being adhered to the surface of the core, the core having a carbon-coated lithium structure, the carbon-coated lithium structure being a layer containing a carbon element at least partially coating the second particles containing a lithium element, the coating shell layer comprising an alginate polymer bonded to the base film, the alginate polymer being configured to swell in the electrolyte during a secondary battery formation stage and cycle to form a plurality of channels for the electrolyte to infiltrate into the surface and interior of the core.
Alternatively, the alginate polymer comprises a calcium alginate polymer.
Alternatively, the particle size of the alginate polymer is 100nm to 300nm.
Alternatively, the thickness of the lithium supplementing coating is 0.8um-2um.
Alternatively, the thickness of the base film is 9um to 16um.
In a second aspect, the present invention provides a method for preparing a separator according to the first aspect, comprising the steps of:
dispersing the carbon-coated lithium powder in water, and then adding a dispersing agent and uniformly stirring to obtain carbon-coated lithium dispersion;
preparing sodium alginate solution and metal chloride salt solution respectively;
setting up an electrostatic spraying device, forming spraying by using a carbon-coated lithium dispersing agent and a sodium alginate solution through the electrostatic spraying device, collecting the spraying in a collecting tank filled with a metal chloride salt solution, and reacting to obtain a lithium supplementing coating;
preparation of the separator:
and coating a lithium supplementing coating on at least one side of the base film to obtain the diaphragm.
Alternatively, the dispersant is selected from polyacrylic acid, ammonium polyacrylate or ammonium polycarboxylate.
Alternatively, the mass concentration of the carbon-coated lithium dispersion is 1% -3%.
As an alternative scheme, the mass concentration of the sodium alginate solution is 7% -10%, and the mass concentration of the metal chloride salt solution is 1% -5%.
Alternatively, the conditions of the electrostatic spray are as follows: the sample injection speed of the carbon-coated lithium dispersion liquid is 0.1-0.5 mL/h, the sample injection speed of the sodium alginate solution is 0.5-1.2 mL/h, the voltage is 1kV-3kV, and the distance between a collecting tank of the metal chloride salt solution and a spray head of the electrostatic spraying device is 5cm-15cm.
In a third aspect, the present invention provides an energy storage device comprising the diaphragm of the first aspect.
In a fourth aspect, the invention provides an electrical consumer, characterized in that the electrical consumer comprises an energy storage device as in the third aspect, the energy storage device powering the electrical consumer.
According to the diaphragm provided by the invention, the lithium supplementing coating adopts particles with a core-shell structure, the carbon-coated lithium structure is taken as a lithium supplementing additive as a core layer, the alginate polymer is taken as a shell layer, the alginate polymer and the base film have good bonding effect, and meanwhile, in the battery formation stage and the cycle process, the alginate polymer swells in the electrolyte to form a plurality of channels which are soaked on the surface and in the interior of the carbon-coated lithium by the electrolyte, so that the electrolyte is in contact with the carbon-coated lithium structure, and the lithium supplementing effect is further achieved. The diaphragm disclosed by the invention can be used for compensating consumed active lithium while ensuring the basic function of the diaphragm to prevent the positive electrode and the negative electrode from being contacted with each other, so that the energy density, the low-temperature performance, the multiplying power performance and the cycle performance of the battery are further improved.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the following drawings, in which:
FIG. 1 is a schematic diagram of an electrostatic spraying device used in the preparation of a diaphragm of the present application;
fig. 2 is a TEM photograph of the lithium-compensating coating prepared in example 1.
Detailed Description
The present application is described in further detail below with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
In a first aspect, embodiments of the present invention provide a separator for a secondary battery including an electrolyte, the secondary battery including a base film and a lithium supplementing coating layer attached to at least one side surface of the base film, the lithium supplementing coating layer including a plurality of first particles having a core-shell structure, the first particles having a core and a coating shell layer on a surface of the core, the coating shell layer being adhered to the surface of the core, the core having a carbon-coated lithium structure in which a layer containing a carbon element at least partially coats a second particle containing a lithium element, the coating shell layer including an alginate polymer adhered to the base film, the alginate polymer being configured to swell in the electrolyte to form a plurality of channels in which the electrolyte wets the surface and inside of the core during a formation stage and a cycle of the secondary battery.
The base film may be any conventional porous base film, for example, a polymer porous base film, a nonwoven fabric, a ceramic film, or the like, wherein the polymer porous base film may be any one or more of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl alcohol, polyamide, polyethylene terephthalate, polyethylene, polypropylene, and derivatives thereof; the embodiments of the present application are not particularly limited thereto. In specific embodiments, the base film may employ a polyolefin porous film, for example, any one of a PP/PE/PP three-layer film, a PP/PP double-layer film, a PE/PE double-layer film, a PP single-layer film, and a PE single-layer film.
The lithium supplementing coating can be directly coated on one side surface of the base film, and the lithium supplementing coating can also be coated on two opposite side surfaces of the base film to obtain the diaphragm.
It is understood that the lithium compensating coating comprises a plurality of first particles having a core-shell structure, wherein the coating shell of the first particles may be any alginic acid polymer such as, but not limited to, calcium alginate polymer, magnesium alginate polymer, etc. The structure of alginic acid enables the metal alginate polymer to have good bonding effect, so that the lithium supplementing coating can be uniformly and well attached to the base film without using other binders, and the alginate polymer swells and disperses in the electrolyte to form a channel for the electrolyte to infiltrate the carbon-coated lithium structure, so that the electrolyte contacts with the carbon-coated lithium structure to supplement active lithium, the membrane is further guaranteed to have good performance, and the lithium ion transmission channel can be provided while the anode and the cathode are guaranteed to be isolated.
The core of the first particle has a carbon-coated lithium structure, which can be approximated as a core-shell structure, i.e., the layer containing the carbon element partially or fully coats the lithium element; the carbon-coated lithium can be directly purchased, has good conductivity, can provide an electron movement channel, is more beneficial to removing active lithium ions, is used for supplementing consumed active lithium, improves the energy density of a battery, and can improve the mechanical property, high-temperature stability and safety performance of a battery diaphragm.
The diaphragm of this application embodiment has solved among the prior art diaphragm function singleness, can't promote the problem of the performance of battery. According to the diaphragm, the lithium supplementing coating adopts a core-shell structure, carbon-coated lithium is used as a lithium supplementing additive to serve as a core layer, an alginate polymer is used as a shell layer, good bonding effect is achieved between the alginate polymer and a base film, and meanwhile a plurality of channels are formed in which electrolyte infiltrates the surface and the inside of the carbon-coated lithium after swelling in the electrolyte, so that the electrolyte is beneficial to contact with the carbon-coated lithium structure, and further the lithium supplementing effect is achieved. The diaphragm can be used for forming an SEI film of the negative electrode while ensuring the basic function of the diaphragm to prevent the positive electrode and the negative electrode from being contacted with each other and compensating consumed active lithium, so that the energy density, the low-temperature performance, the multiplying power performance and the cycle performance of the battery are improved.
As a practical matter, the alginate polymer comprises a calcium alginate polymer. In the embodiment, the calcium alginate polymer is stable, is not easy to react with electrolyte, has a good bonding effect, can well buffer lithium ions, and can rapidly release the lithium ions coated inside after being swelled by the electrolyte, so that consumed lithium is effectively supplemented.
As a practical way, the particle size of the alginate polymer is 100nm-300nm, and the particle size of the carbon-coated lithium is 500nm-10um. Wherein the particle size of the alginate polymer may be 100nm, 200nm or 300nm; the particle size of the carbon-coated lithium is 500nm, 600nm, 700nm, 800nm, 900nm or 10um. The particle size of the carbon-coated lithium and the alginate polymer in the embodiment is favorable for ensuring proper viscosity of the lithium supplementing coating and can well release active lithium. When the particle size of the alginate polymer is smaller than 100nm, the pore is easy to be blocked, so that the lithium supplementing effect is poor, and when the particle size of the alginate polymer is larger than 300nm, the viscosity of a shell layer is too large, and lithium ions cannot be reliably released; when the particle size of the carbon-coated lithium is larger than 10um, the cohesiveness is poor, the lithium supplementing coating is easy to fall off, and when the particle size of the carbon-coated lithium is smaller than 500nm, the lithium supplementing effect is poor.
As a practical way, the thickness of the lithium supplementing coating is 0.8um-2um. The thickness of the lithium-compensating coating refers to the total thickness of the lithium-compensating coating on the base film, for example, when the lithium-compensating coating is attached to one side of the base film, the thickness of the lithium-compensating coating is one side; when the lithium supplementing coating is attached to both sides of the base film, the sum of the lithium supplementing coatings on both sides is obtained. The thickness of the lithium supplementing coating can be any value in the range, such as 0.8um, 1um, 1.5um or 2um, and the like, and the thickness of the lithium supplementing layer is moderate, so that lithium supplementing can be reliably realized, meanwhile, the transmission of lithium ions is ensured, the problems that the thickness of the lithium supplementing layer is too thin, the lithium supplementing effect cannot meet the requirement, the thickness of the lithium supplementing layer is too thick, the transmission of lithium ions is influenced, the volume energy density and the quality energy density of a battery cell are reduced, and the cost is increased are effectively avoided.
As a practical way, the thickness of the base film is 9um to 16um. The thickness of the base film may be 9um, 12um, 13um, 15um, 16um, or the like. The thickness of the base film in the embodiment is safe and reliable, meanwhile, effective transmission of lithium ions can be guaranteed, and the problems that the thickness of the base film is too thin, the safety cannot meet requirements, the thickness of the base film is too thick, the transmission performance of lithium ions is affected, the volume energy density of an electric core is reduced, and the cost is increased are effectively avoided.
In summary, the diaphragm of this application, the lithium supplementing coating adopts core-shell structure to carbon package lithium is as the lithium supplementing additive and is regarded as the nuclear layer, and alginate polymer is regarded as the shell layer, has fine bonding effect between alginate polymer and the base film, forms a plurality of passageways that electrolyte infiltration carbon package lithium surface and inside after swelling in the electrolyte simultaneously to be favorable to electrolyte and with carbon package lithium structure contact, and then play the lithium supplementing effect. The diaphragm can be used for forming an SEI film of the negative electrode while ensuring the basic function of the diaphragm to prevent the positive electrode and the negative electrode from being contacted with each other and compensating consumed active lithium, so that the energy density, the low-temperature performance, the multiplying power performance and the cycle performance of the battery are improved.
In a second aspect, the present invention provides a method for preparing a separator, comprising the steps of:
s1, dispersing carbon-coated lithium powder in water, and then adding a dispersing agent and uniformly stirring to obtain carbon-coated lithium dispersion;
wherein, the carbon-coated lithium can be directly purchased as commercial carbon-coated lithium powder.
Dissolving sodium alginate powder in deionized water, adding a dispersing agent, and uniformly stirring, wherein the dispersing agent can be any dispersing agent, and the stirring mode can be any mode, such as magnetic stirring, stirring by a stirrer and the like; in a specific embodiment, 10g of sodium alginate powder is dissolved in 90ml of deionized water, stirred at 1000r/min for 1h and then loaded into a 10ml syringe for standby;
s2, preparing sodium alginate solution and metal chloride salt solution respectively;
wherein, the metal chloride salt solution can be calcium chloride solution, magnesium chloride solution and the like, and the embodiment of the application is not particularly limited;
illustratively, 10g sodium alginate powder is dissolved in 90ml deionized water, stirred at 1000r/min for 1h and then loaded into a 10ml syringe for use;
3g of calcium chloride powder is dissolved in 97ml of deionized water, stirred for 1h at 1000r/min and then loaded into a receiver for standby;
and S3, as shown in fig. 1, constructing an electrostatic spraying device, forming spraying by using a carbon-coated lithium dispersing agent and a sodium alginate solution through the electrostatic spraying device, and collecting the spraying in a collecting tank filled with a metal chloride salt solution for reaction to obtain a diaphragm.
The electrostatic spraying device is a coaxial electrostatic spraying device and comprises a first sample injector, a second sample injector, a spray head, a collecting tank and a power supply, wherein the first sample injector and the second sample injector are respectively used for containing carbon-coated lithium dispersion liquid and sodium alginate solution, the electrostatic spraying device is opened for sample injection according to preset flow, the first sample injector and the second sample injector respectively sample the carbon-coated lithium dispersion liquid and the sodium alginate solution to the spray head, the spray head atomizes the carbon-coated lithium dispersion liquid and the sodium alginate solution to form spray drops, the spray drops drop in a calcium chloride collecting tank are compatible with calcium chloride, and a stable crosslinked calcium alginate coated carbon-coated lithium supplementing coating can be formed after the sodium alginate and calcium ions are crosslinked.
Preparation of the separator:
and coating a lithium supplementing coating on at least one side of the base film to obtain the diaphragm.
In conclusion, the embodiment of the application adopts the electrostatic spraying mode to obtain the lithium supplementing coating, the electrostatic spraying mode is simple to operate and easy to realize, the structural growth of the lithium supplementing coating is facilitated, the uniformity of particles of the lithium supplementing coating can be ensured, and further the battery performance of the diaphragm is improved.
As a practical matter, the dispersant is selected from polyacrylic acid, ammonium polyacrylate salts or ammonium polycarboxylic acid salts. The dispersing agent adopted in the embodiment is beneficial to ensuring that carbon-coated lithium is uniformly dispersed, and agglomeration is not caused, so that the preparation of a lithium supplementing coating is facilitated.
As a practical way, the mass concentration of the carbon-coated lithium dispersion liquid is 1% -3%. Wherein the mass concentration of the carbon-coated lithium dispersion liquid can be 1%, 2% or 3% and the like. If the concentration of the carbon-coated lithium dispersion is less than 1%, it may cause a decrease in spray efficiency, and if the concentration of the carbon-coated lithium dispersion is more than 3%, it may block the spray hole of the spray head; the concentration of the carbon-coated lithium dispersion liquid of the present embodiment is advantageous in ensuring the spray efficiency, and the spray hole is not blocked.
As a realizable mode, the mass concentration of the sodium alginate solution is 7% -10%, and the mass concentration of the metal chloride salt solution is 1% -5%. Wherein the concentration of the sodium alginate solution can be 7%, 8%, 9% or 10%; the mass concentration of the metal chloride salt solution can be 1%, 2%, 3%, 4% or 5%; the concentration of the sodium alginate solution of the embodiment of the application is favorable for guaranteeing the spraying efficiency, and the concentration of the metal chloride salt is favorable for forming calcium alginate polymer with sodium alginate, so that the formation of the lithium supplementing coating with the core-shell structure is favorable.
As a practical way, the conditions of electrostatic spraying are as follows: the sample injection speed of the carbon-coated lithium dispersion liquid is 0.1-0.5 mL/h, the sample injection speed of the sodium alginate solution is 0.5-1.2 mL/h, the voltage is 1kV-3kV, and the distance between a collecting tank of the metal chloride salt solution and a spray head of the electrostatic spraying device is 5cm-15cm. The sample injection speed of the carbon-coated lithium dispersion liquid can be 0.1mL/h, 0.2mL/h, 0.3mL/h, 0.4mL/h or 0.5mL/h; the sample injection speed of the sodium alginate solution is 0.5mL/h, 0.6mL/h, 0.7mL/h, 0.8mL/h, 0.9mL/h, 1.0mL/h or 1.2mL/h; the sample injection speed of the embodiment is moderate, which is beneficial to ensuring the uniform growth of the lithium supplementing coating and avoiding the phenomena that the sample injection speed is too high to easily produce accumulation and too low to ensure the spraying effect; the voltage can be 1kV, 2kV or 3kV, and the voltage range disclosed in the embodiment is beneficial to ensuring that the carbon-coated lithium dispersion liquid and the sodium alginate solution are uniformly sprayed out, and the operation is safe; the range of the distance between the collecting tank of the metal chloride salt solution and the spray head of the electrostatic spraying device is favorable for ensuring that the carbon-coated lithium dispersion liquid and the sodium alginate solution are atomized and are in uniform contact with and compatible with calcium chloride, so that the lithium supplementing layer is ensured to be uniformly distributed.
In summary, according to the method disclosed by the embodiment of the application, the lithium supplementing coating is formed on the surface of the base film through the electrostatic spraying technology, the operation is simple and controllable, the lithium supplementing coating with the core-shell structure can be prepared through regulating and controlling electrostatic spraying conditions and the like, further, the swelling of the diaphragm and the electrolyte in the working process of the battery is effectively ensured, active lithium is released to compensate consumed active lithium, and the energy density and the cycle life of the lithium ion battery are further improved.
In a third aspect, the present invention provides an energy storage device comprising the diaphragm of the first aspect. It will be appreciated that the energy storage device has all the features and advantages of the diaphragm described above and will not be described in detail herein. Overall, the energy storage device has a high energy density and good cycle performance.
In a specific embodiment, the energy storage device may be a lithium ion battery, including a positive electrode sheet, a negative electrode sheet, and a separator of the second aspect, where the positive electrode sheet and the negative electrode sheet are located on two sides of the separator, respectively. The positive electrode can be made of lithium iron phosphate material, the negative electrode can be made of graphite material, and after the battery core is assembled, the battery core is activated in the formation stage, and negative pressure is generated during activation so as to remove gas, and finally, the battery core is manufactured through the procedures of capacity, OCV and the like.
In a fourth aspect, the invention provides an electrical consumer, characterized in that the electrical consumer comprises the energy storage device of the third aspect, the energy storage device supplying power to the electrical consumer. For example, the powered device may be an electric vehicle or the like. Therefore, the electric equipment has all the characteristics and advantages of the diaphragm, and the details are not repeated here.
The present invention will be illustrated by the following examples, which are given for illustrative purposes only and are not intended to limit the scope of the present invention in any way, and unless otherwise specified, the conditions or procedures not specifically described are conventional and the reagents and materials employed are commercially available.
The lithium ions of examples 1-6 and comparative examples 1-2 were prepared as follows:
example 1
Preparation of the separator:
dispersing 1g of carbon-coated lithium powder in 99mL of water, adding 1% polyacrylic acid (0.01 g) as a dispersing agent, stirring for 1h at 1800r/min to obtain carbon-coated lithium dispersion, and filling into a 10mL syringe for later use;
dissolving 10g of sodium alginate powder in 90mL of deionized water, stirring at 1000r/min for 1h, and loading into a 10mL syringe for later use;
3g of calcium chloride powder is dissolved in 97mL of deionized water, stirred for 1h at 1000r/min and then loaded into a receiver for standby;
setting up an electrostatic spraying device, forming spraying by using a carbon-coated lithium dispersing agent and a sodium alginate solution through the electrostatic spraying device, wherein the sample injection speed of the carbon-coated lithium dispersing agent is 0.3mL/h, the sample injection speed of the sodium alginate solution is 0.8mL/h, the voltage is 1.8kV, the receiving distance is 5-15cm, and the spraying is collected in a collecting tank filled with a metal chloride salt solution and reacts to obtain a lithium supplementing coating;
preparation of the separator:
coating lithium supplementing coating layers on two sides of a PP16 base film to obtain a diaphragm (a diaphragm coated with calcium alginate and coated with carbon);
preparation of the battery:
graphite is used as a negative electrode material, lithium iron phosphate is used as a positive electrode material, a coating diaphragm with a lithium supplementing function, electrolyte and the like are assembled into a battery cell, activation is carried out in a formation stage, and negative pressure is pumped during activation so as to remove gas; and finally, manufacturing a finished battery cell through procedures of capacity, OCV and the like, and assembling the battery.
Example 2
Unlike example 1, the thickness of the lithium-compensating coating layer in this example was 1um;
example 3
Unlike example 1, the thickness of the lithium-compensating coating layer in this example was 1.5um;
example 4
Unlike example 1, the thickness of the lithium-compensating coating layer in this example was 2um;
example 5
Unlike example 1, the thickness of the lithium-compensating coating layer in this example was 0.1um;
example 6
Unlike example 1, the thickness of the lithium-compensating coating layer in this example was 4um;
comparative example 1
Unlike example 1, the separator used in this comparative example was a PP16 separator;
comparative example 2
Unlike example 1, the separator used in this comparative example was a PP16+ PVDF coating;
TABLE 1 physical Properties parameters of the separator in examples 1-6 and comparative examples 1-2
Wherein,,
areal density refers to the mass per unit area of a substance of a certain thickness; the test method is as follows: the wafer with a certain area is punched and placed in an electronic balance for weighing, and the obtained weight/area of the wafer is the area density value;
air permeability refers to the degree to which an object or medium allows gas to pass through; and the air permeability is obtained through testing by an air permeability tester.
From the data in table 1, it can be seen that as the separator thickness increases, the areal density and air permeability increase, which primarily affects electron transport, and that a greater areal density and air permeability increases the internal resistance of the cell, resulting in a decrease in the rate capability of the cell.
The performance test procedure and test results of the lithium ion battery are described below:
(1) Low temperature performance test: at 25 o Standing for 1 hr, discharging 1C constant current to 2.5V, charging 1C constant current to 3.65V, and constant voltage charging to cut-off current of 0.05C, standing for 30min, discharging 1C constant current to 2.5V (25.) o Initial discharge capacity below), standing for 30min, charging to 3.65V with 1C constant current, constant voltage charging to 0.05C cutoff current (immediately setting the temperature of the high-low temperature box to-20 ℃ after completion), standing for 5h, cooling to-20 ℃ of the temperature sensing line on the surface of the battery core, rest for 2h, discharging to 2.0V with 1C constant current, and recording as-20V o Lower discharge capacity; -20 ℃ capacity retention = -20 discharge capacity/25 o Discharge capacity.
(2) And (3) testing the cycle performance: charging the battery to 3.65V at a constant current of 1C, then charging to 0.05C at a constant voltage, standing for 30min, discharging to 2.5V at a constant power of 1C, recording as a charge-discharge cycle, and performing 1000 cycles according to the conditions; capacity retention (%) = (discharge capacity of 1000 th cycle/discharge capacity of first cycle) ×100% after 1000 cycles/3.65V cycle of the battery.
(3) And (3) multiplying power performance test: standing the battery for 30min, charging to 3.65V at a constant current of 1C, charging to 0.05C at a constant voltage, standing for 30min, and discharging to 2.5V at a constant power of 1C, wherein 1C is the initial discharge capacity; as in the 1C test procedure, one charge-discharge cycle was recorded with 2C discharge, and the 2C discharge capacity retention rate=2C discharge capacity/1C discharge capacity.
Table 2 test results of the batteries of examples 1 to 6 and comparative examples 1 to 2
As can be seen from the electron micrograph of fig. 2, the coating of example 1 of the present application is a typical core-shell structure, wherein the inside of the dotted line is a core of a carbon-coated lithium structure, the outside of the dotted line is a shell layer of calcium alginate polymer, and the particle size of the shell layer of calcium alginate polymer is about 300nm.
According to the results shown in Table 2;
the battery properties of examples 1 to 6 are obviously superior to those of comparative examples 1 and 2 in terms of the capacity retention at-20C, the 2C discharge capacity retention, the 1000-cycle capacity retention and the 2.5V first coulombic efficiency, due to the battery properties of comparative examples 1 and 2, thus demonstrating that the separator of the present application example can effectively improve the low temperature properties, rate properties, capacity properties and cycle properties of the battery.
In combination with the data of examples 1-6, the battery performance of examples 1-4 is obviously due to the battery performance of examples 5 and 6, which shows that the thickness of the lithium supplementing coating layer of the embodiment of the application is moderate, and lithium supplementing can be reliably realized, meanwhile, the transmission of lithium ions is ensured, and further, the battery performance is improved.
The foregoing description is only of the preferred embodiments of the present application and is presented as a description of the principles of the technology being utilized. It will be appreciated by persons skilled in the art that the scope of the invention referred to in this application is not limited to the specific combinations of features described above, but it is intended to cover other embodiments in which any combination of features described above or equivalents thereof is possible without departing from the spirit of the invention. Such as the above-described features and technical features having similar functions (but not limited to) disclosed in the present application are replaced with each other.
Claims (12)
1. A separator for a secondary battery comprising an electrolyte, comprising a base film and a lithium-compensating coating layer attached to at least one side surface of the base film, the lithium-compensating coating layer comprising a plurality of first particles having a core-shell structure, the first particles having a core and a cladding shell layer on the surface of the core, the cladding shell layer adhering to the surface of the core, the core having a carbon-coated lithium structure in which a layer containing elemental carbon at least partially coats a second particle containing elemental lithium, the cladding shell layer comprising an alginate polymer bonded to the base film, the alginate polymer being configured to swell in the electrolyte to form a plurality of channels for electrolyte infiltration to the surface and interior of the core during formation and cycling of the secondary battery.
2. The separator of claim 1, wherein the alginate polymer comprises a calcium alginate polymer.
3. The membrane of claim 1, wherein the alginate polymer has a particle size of 100nm to 300nm.
4. The separator of claim 1, wherein the lithium-compensating coating has a thickness of 0.8um-2um.
5. The membrane of claim 1, wherein the base film has a thickness of 9um to 16um.
6. A method of producing a separator according to any one of claims 1 to 5, comprising the steps of:
preparation of a lithium supplementing coating:
dispersing the carbon-coated lithium powder in water, and then adding a dispersing agent and uniformly stirring to obtain carbon-coated lithium dispersion;
preparing sodium alginate solution and metal chloride salt solution respectively;
building an electrostatic spraying device, forming spraying by the carbon-coated lithium dispersing agent and the sodium alginate solution through the electrostatic spraying device, and collecting and reacting the spraying in a collecting tank filled with the metal chloride salt solution to obtain the lithium supplementing coating;
preparation of the separator:
and coating the lithium supplementing coating on at least one side of the base film to obtain the diaphragm.
7. The method of claim 6, wherein the dispersant is selected from the group consisting of polyacrylic acid, ammonium salts of polyacrylic acid, and ammonium salts of polycarboxylic acid.
8. The method of claim 6, wherein the carbon-coated lithium dispersion has a mass concentration of 1% -3%.
9. The method according to claim 6, wherein the sodium alginate solution has a mass concentration of 7% -10% and the metal chloride salt solution has a mass concentration of 1% -5%.
10. The method of claim 6, wherein the electrostatic spraying conditions are as follows: the sample injection speed of the carbon-coated lithium dispersion liquid is 0.1-0.5 mL/h, the sample injection speed of the sodium alginate solution is 0.5-1.2 mL/h, the voltage is 1kV-3kV, and the distance between a collecting tank of the metal chloride salt solution and a spray head of the electrostatic spraying device is 5cm-15cm.
11. Energy storage device, characterized in that it comprises a membrane according to any one of claims 1-5.
12. A powered device comprising the energy storage device of claim 11, the energy storage device powering the powered device.
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