CN107681114B - Positive plate, preparation process and lithium slurry battery containing positive plate - Google Patents
Positive plate, preparation process and lithium slurry battery containing positive plate Download PDFInfo
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- CN107681114B CN107681114B CN201610620726.4A CN201610620726A CN107681114B CN 107681114 B CN107681114 B CN 107681114B CN 201610620726 A CN201610620726 A CN 201610620726A CN 107681114 B CN107681114 B CN 107681114B
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- positive electrode
- active layer
- lithium
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 239000002002 slurry Substances 0.000 title claims abstract description 50
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- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical class [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 2
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical class [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 claims description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 2
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical class [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical class [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 2
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical class [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 2
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- JVZGJLAPJLXQKT-UHFFFAOYSA-N lithium iron(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Fe+2].[Mn+2].[Li+].[Ni+2] JVZGJLAPJLXQKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
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- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims description 2
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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
- 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
- H01M4/624—Electric conductive fillers
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium slurry battery positive plate, which comprises a porous current-collecting positive plate layer, a positive active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current-collecting positive plate layer and the positive active layer, wherein the positive active layer is positioned between the two porous current-collecting positive plate layers; before lithium thick liquids battery and the injection electrolyte are advanced in the equipment to this positive plate, the anodal active layer in the positive plate contains the fixed anodal electrically conductive granule of part or whole non-bonding, and the battery just annotates liquid when using and forms thick liquids and activate the battery simultaneously, has avoided the requirement of thick liquids filling to special equipment and environment, and the deposit and the transportation of the battery module of being convenient for have application prospect in large-scale energy storage power station and for military use civilian deposit power. Meanwhile, the invention also provides a preparation process of the battery positive plate and a lithium slurry battery containing the positive plate.
Description
Technical Field
The invention belongs to the technology of chemical power batteries, and particularly relates to a lithium slurry battery positive plate, a preparation process thereof and a lithium slurry battery containing the positive plate.
Background
Lithium ion batteries are novel high-energy batteries using lithium intercalation compounds as positive and negative electrode materials, and have a series of advantages of high specific energy, high voltage, small self-discharge, good cycle performance, long service life and the like compared with lead-acid batteries and nickel-hydrogen batteries, and are receiving more and more attention.
The lithium slurry battery comprises an electrode plate and electrolyte, conductive slurry is formed inside a positive plate and/or a negative plate of the battery after the electrolyte is injected, the conductive slurry contains conductive particles which are suspended or precipitated in the electrolyte in a certain proportion, when the battery is impacted or vibrated from the outside, the conductive particles can move in the electrolyte and form a dynamic conductive network because the conductive particles are not bonded and fixed, and the conductive particles can only contain a conductive agent or can be composite particles of an active material and the conductive agent. The conductive paste in the lithium paste battery can avoid battery capacity reduction and cycle life attenuation caused by falling or loosening of electrode materials.
Disclosure of Invention
The invention provides a lithium slurry battery positive plate and a lithium slurry battery containing the positive plate. Meanwhile, the invention also provides a preparation process of the positive plate.
The technical scheme provided by the invention is as follows:
a positive plate of a lithium slurry battery comprises a porous current-collecting positive plate, a positive active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current-collecting positive plate and the positive active layer, wherein the positive active layer is positioned between the two porous current-collecting positive plates; the positive electrode active layer contains part or all of positive electrode conductive particles which are fixed in a non-bonding mode, and the positive electrode conductive particles are conductive agents, or the positive electrode conductive particles are compounds or mixtures of positive electrode active materials and the conductive agents.
When the positive electrode conductive particles are a compound or mixture of a positive electrode active material and a conductive agent, the positive electrode active material and the conductive agent are compounded or mixed in a surface coating, bonding, mechanical mixing or the like.
The positive active layer contains part or all of the non-adhesive fixed positive conductive particles, and can be in a semi-dry state containing part of liquid, such as paste, slurry, colloid or gel; preferably, the positive electrode active layer is in a completely dry state, i.e. a dry stacked state of the positive electrode conductive particles, such as powder, pressed sheet, pressed block, etc., and the porosity of the stacked state is greater than 5% and less than 60%. And adopting a dry positive active layer, and fully infiltrating the positive conductive particles with the electrolyte after injecting the electrolyte, so that conductive slurry is formed inside the positive plate. The positive plate is suitable for flow line production, can be realized by partial modification on the basis of the existing lithium battery liquid injection equipment, and has high consistency and better commercial prospect.
The positive electrode active layer comprises positive electrode conductive particles and/or a binder, the thickness of the positive electrode active layer is 0.5-10 mm, the average particle size of the positive electrode conductive particles is 0.05-500 mu m, the positive electrode conductive particles are a compound or a mixture of a positive electrode active material and a conductive agent, and the mass ratio of the positive electrode active material to the conductive agent is preferably 20-98: 80-2, and the mass ratio of the binder is not more than 10%.
Or the positive active layer comprises a first positive active layer and a second positive active layer, the thickness of the positive active layer is 0.5-10 mm, and the thickness of the first positive active layer is not less than 0.05mm and not more than 10 mm; the positive electrode active layer comprises a positive electrode active material, a conductive agent and a binder, wherein the positive electrode conductive particles in the first positive electrode active layer are partially or completely positioned on the surface or in meshes of the porous positive electrode current collecting layer, the positive electrode active layer comprises the positive electrode active material, the conductive agent and the binder, and the positive electrode active material, the conductive agent and the binder are uniformly mixed according to the mass ratio of 59-98: 1-40: 1-10; the second positive electrode active layer is in close contact with the first positive electrode active layer, the second positive electrode active layer comprises non-adhesive fixed positive electrode conductive particles, the average particle size of the positive electrode conductive particles is 0.05-500 mu m, the mass ratio of the positive electrode active material to the conductive agent is preferably 0-98: 100-2 under the condition that the positive electrode conductive particles are a compound or a mixture of the positive electrode active material and the conductive agent, and the mass ratio of the binder is not more than 5%. That is, when the positive electrode active layer includes the first positive electrode active layer and the second positive electrode active layer, the positive electrode conductive particles in the second positive electrode active layer may contain no positive electrode active material and only a conductive agent.
When the positive active layer includes the first positive active layer and the second positive active layer, it may better provide energy of the battery at a large rate since the first positive active layer is in better conductive contact with the porous current collecting positive layer.
The positive active material of the positive active layer is one or more of lithium iron phosphate, lithium manganese phosphate, lithium silicate, lithium iron silicate, sulfate compounds, sulfur-carbon compounds, elemental sulfur, titanium sulfur compounds, molybdenum sulfur compounds, iron sulfur compounds, doped lithium manganese oxides, lithium cobalt oxides, lithium titanium oxides, lithium vanadium oxides, lithium nickel manganese oxides, lithium nickel cobalt aluminum oxides, lithium nickel cobalt manganese oxides, lithium iron nickel manganese oxides and other lithium-intercalatable compounds. The binder is a polymer material which has a wide potential window and is stable to positive and negative electrode active materials and electrolyte, and the polymer material can be one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyterephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene-butadiene rubber, sodium carboxymethylcellulose, modified polyolefin, polyacetylene, polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, poly (p-phenylene) and derivatives thereof, and polyfluorene and derivatives thereof. The conductive agent is one or more of carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers, amorphous carbon or metal conductive particles.
The positive conductive particles in the positive active layer are partially or completely positioned in pores of the porous current collecting positive layer, the porous current collecting positive layer is an electronic conductive layer with a thickness of 0.01-2000 mu m and a through hole structure, the through hole porosity is 10-90%, and the pore size range is 0.05-2 mm. The porous current-collecting positive electrode layer is a metal conducting layer, the metal conducting layer is a metal net or a metal wire woven net, and meshes of the metal conducting layer are square, rhombic, rectangular or polygonal; or the metal conducting layer is a porous foam metal layer with a porous structure; alternatively, the metal conductive layer is formed by mechanically stamping or chemically etching a metal plate or a metal foil, and the material of the metal conductive layer is aluminum, aluminum alloy, stainless steel, silver, tin, titanium, or the like, preferably the material is aluminum. Or the porous current-collecting positive electrode layer is made of carbon fiber conductive cloth or conductive cloth formed by mixing metal wires and organic fiber wires, and the metal wires are made of copper, nickel or titanium and the like. Or, the porous current-collecting positive electrode layer is a metal conductive layer, a conductive cloth, a porous organic material or a microporous inorganic non-metallic material, the surface of which is coated with a conductive coating or plated with a metal film, the porous organic material comprises natural cotton hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene, polytetrafluoroethylene and the like, the microporous inorganic non-metallic material comprises glass fiber non-woven fabrics, ceramic fiber paper and the like, the conductive coating or the metal film is made of aluminum, alloy aluminum, stainless steel, silver and the like, and preferably the material is aluminum. Or the porous current-collecting positive electrode layer is a composite layer of a metal conducting layer, conducting cloth, a porous organic material, an inorganic non-metal material, a metal conducting layer with a conducting coating or a metal film coated on the surface, conducting cloth, an inorganic non-metal material, a porous organic material and a polymer electrolyte, and the polymer electrolyte is a gel polymer electrolyte composite material formed by compounding a polymer matrix, a liquid organic plasticizer and lithium salt. Or the porous current collecting positive electrode layer is a combination of any two or more of the above.
Preferably, the grid of the porous current collecting positive electrode layer contains an interface improvement layer. The material of the interface improvement layer comprises a conductive agent and a binder, wherein the mass ratio of the binder to the conductive agent is (0.5-20): 99.5 to 80, or the interface improving layer only comprises a conductive agent; the conductive agent is one or more of carbon black, ketjen black, graphene, carbon nano tubes, carbon fibers, amorphous carbon or metal conductive particles, the binder is a polymer material which has a wide potential window and is stable to positive and negative electrode active materials and electrolyte, and the polymer material can be one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyterephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene butadiene rubber, sodium carboxymethylcellulose, modified polyolefin, polyacetylene, polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polyterenylene and derivatives thereof, polyterephlene and derivatives thereof, and polyfluorene and derivatives thereof.
The interface improving layer is tightly compounded on the grid of the porous current collecting positive electrode layer, so that the interface performance of the porous current collecting positive electrode layer can be improved, and the interface resistance between the porous current collecting positive electrode layer and the positive electrode active layer is reduced. In the present invention, the preferred interface-improving layer is thin, is only present at the grid of the porous current-collecting positive electrode layer, and may not be distributed in the pores of the porous current-collecting positive electrode layer. The compounding mode of the interface improving layer and the porous afflux positive electrode layer includes but is not limited to one or more of vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, mechanical pressing, printing and ink-jet printing.
When the pore space of the porous current collecting positive electrode layer is large, the phenomenon of material leakage can occur when the interface improving layer is compounded at the grid of the porous current collecting positive electrode layer and when the positive electrode conductive particles in the intermediate-dryness positive electrode active material layer fall into the pore space of the porous current collecting positive electrode layer, therefore, preferably, the porous current collecting positive electrode layer further comprises a leakage-proof organic porous layer, the leakage-proof organic porous layer is compounded at one side or two sides of the porous current collecting positive electrode layer, or the leakage-proof organic porous layer can be arranged in the middle of the porous current collecting positive electrode layer when the porous current collecting layer has a double-layer or multi-layer structure, and the leakage can be prevented by the existence of the leakage-proof organic porous layer. The material of the leak-proof organic porous layer can be carbon fiber conductive cloth, conductive cloth mixed by metal wires and organic fiber wires, or natural cotton-flax, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene fine mesh cloth, glass fiber non-woven cloth, ceramic fiber paper and the like, or conductive cloth, fine mesh cloth, glass fiber non-woven cloth and ceramic fiber paper with the surfaces coated with conductive coatings or plated with metal films, so that the leak-proof organic porous layer and the porous positive electrode current collecting layer can jointly play a current collecting role, the aperture and the thickness of the leak-proof organic porous layer are smaller than those of the porous current collecting positive electrode layer, the range of the leak-proof organic porous layer is 10-800 mu m, the thickness of the leak-proof organic porous layer is 0.01-1000 mu m, and the porosity of the leak-.
Furthermore, the conductive layer can be added on the surface of the positive active layer in a suction filtration, spraying and other modes, so that the conductive layer can be partially or completely filled in the pores of the positive active layer, and particles in the positive active layer are better ensured to be in a conductive network all the time. When the positive electrode active layer includes the first positive electrode active layer and the second positive electrode active layer and the positive electrode conductive particles of the second positive electrode active layer contain only the conductive agent, the second positive electrode active layer itself becomes a conductive layer.
The conductive layer comprises a conductive agent and/or a binder, the mass ratio of the binder to the conductive agent is 0-10: 100-90, and the conductive layer preferably does not contain the binder. The binder is a polymer material which has a wide potential window and is stable to positive and negative electrode active materials and electrolyte, the polymer material can be one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyterephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene-butadiene rubber, sodium carboxymethylcellulose, modified polyolefin, polyacetylene, polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polyterelene and derivatives thereof, polytereene and derivatives thereof, polyfluorene and derivatives thereof, the conductive agent is one or more of carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers, amorphous carbon or metal conductive particles, and preferably the carbon fibers are compatible with other particle types.
And the peripheral edges of the porous current collecting positive electrode layer, the positive electrode active layer and the porous current collecting positive electrode layer are provided with insulating sealing frames, and the insulating sealing frames are connected to the periphery of the sandwich composite structure in a hot pressing, sticking and other modes. The insulating sealing frame plays a role in insulation and sealing for preventing the positive electrode conductive particles from leaking from the peripheral edge. The material of the insulating sealing frame is a polymer material which is insulating and electrolyte-resistant, such as one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyester terephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene butadiene rubber, sodium carboxymethylcellulose and modified polyolefin.
Preferably, the surface of the positive plate can be provided with a positive isolating layer and/or a negative isolating layer which are electrically insulated and ion-conducted, wherein the positive isolating layer and/or the negative isolating layer are made of polyethylene, polypropylene, polyvinylidene fluoride or other porous polymer materials which are electrically non-conductive; or the isolating layer is glass fiber non-woven fabric, synthetic fiber non-woven fabric, ceramic fiber paper or other electronic non-conductive composite porous materials of inorganic non-metallic materials and organic polymers; or the material of the isolation layer is a gel polymer electrolyte composite material formed by compounding an electronic non-conductive polymer matrix, a liquid organic plasticizer and lithium salt, and further, the pores of the electronic non-conductive porous polymer material, the inorganic non-metallic material and the organic polymer composite porous material are impregnated with an ion-conductive electrolyte or a polymer colloid material.
The invention also provides a preparation process of the lithium slurry battery positive plate, which is characterized in that a positive active layer is positioned between two porous current collecting positive layers, and the prepared positive active layer in the positive plate contains part or all of non-adhesive fixed positive conductive particles, and the preparation process comprises the following steps:
(1) raw material pretreatment: spraying and ultrasonically cleaning the porous current-collecting positive electrode layer by using a cleaning solvent, and drying for later use; drying the required conductive agent, the positive electrode active material and the binder for later use; wherein the drying temperature of the binder is lower than the softening point of the binder material by 20 ℃, the drying time is not more than 2 hours, the drying temperature of the conductive agent and the positive active material can be 100-250 ℃, and the drying time is 2-4 hours;
(2) preparing positive active layer slurry: weighing the positive active material, the conductive agent and the binder required by the porous positive material layer according to the proportion, and uniformly stirring and mixing the positive active material, the conductive agent and the binder to obtain positive active layer slurry;
(3) coating a positive electrode active layer: uniformly and intermittently coating the slurry of the positive electrode active layer obtained in the step (2) on one side of a porous current collecting positive electrode layer through a coating machine so as to form a plurality of coating areas;
(4) and turning over the slices: slicing two adjacent coating areas in the step (3) as a slicing unit, folding the sliced unit from the middle to form quasi-pole pieces, wherein the uncoated surface of the porous current collecting positive electrode layer of each quasi-pole piece faces outwards;
(5) and pressurizing and drying: properly pressurizing the upper surface and the lower surface of the quasi-pole piece by using a clamping plate, wherein the pressure is 0.01-2 MPa, then placing the quasi-pole piece in a high-temperature oven for drying, wherein the drying temperature is 100-140 ℃, the drying time is 2-24 h, the dried quasi-pole piece is naturally cooled to the room temperature in the oven, and the positive active layer in the dried pole piece is in a dry state;
(6) edge packaging: and welding and packaging the four sides of the quasi-pole piece by using an ultrasonic welding machine, and adding an insulating frame by hot pressing to obtain the positive pole piece.
In the step (1), after the porous current collecting positive electrode layer is cleaned and dried, the interface improving layer is compounded at the grid of the porous current collecting positive electrode layer by one or more of vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, mechanical pressing, printing or ink-jet printing.
In the step (1), after the porous current collecting positive electrode layer is cleaned and dried, the leakage-proof organic porous layer is compounded on one side or two sides of the porous current collecting positive electrode layer or the middle of the double-layer or multi-layer structure of the porous current collecting positive electrode layer in a mechanical pressing, bonding and coating mode.
In the step (2), the positive active layer slurry includes a first positive active layer slurry and a second positive active layer slurry, wherein the first positive active layer slurry is in close contact with the porous current-collecting positive layer through one or more of vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, mechanical pressing, printing or ink jet printing, and the second positive active layer slurry is in contact with the first positive active layer slurry through one or more of vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, mechanical pressing, printing or ink jet printing.
And (4) adding a conductive layer on the surface of the positive active layer in a spraying or suction filtration mode between the step (3) and the step (4).
The invention also provides a lithium slurry battery containing the positive plate, which comprises a battery cell and is characterized in that the battery cell comprises a plurality of positive plates and negative plates which are alternately arranged, the distance between the positive plates and the negative plates is 0.05-1 mm, the distance forms an isolation cavity, and the isolation cavity is filled with electrolyte;
the positive plate comprises a porous current-collecting positive layer, a positive active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current-collecting positive layer and the positive active layer, wherein the positive active layer is positioned between the two porous current-collecting positive layers; the positive electrode active layer contains part or all of non-adhesive fixed positive electrode conductive particles, and the positive electrode conductive particles are conductive agents, or the positive electrode conductive particles are compounds or mixtures of positive electrode active materials and the conductive agents;
the negative plate comprises a porous current-collecting negative layer, a negative active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current-collecting negative layer and the negative active layer, wherein the negative active layer is positioned between the two porous current-collecting negative layers; the negative electrode active layer is a metal lithium sheet, or the negative electrode active layer contains part or all of non-bonding fixed negative electrode conductive particles, and the negative electrode conductive particles are a compound or a mixture of a lithium-embeddable negative electrode active material and a conductive agent; the lithium-embeddable negative electrode active material comprises one or more of graphite, hard carbon, soft carbon, tin-based alloy, aluminum-based alloy, lithium titanate or silicon-based material.
And after the battery core is assembled, dehumidified and vacuumized, electrolyte is injected, enters the isolation cavity, and then permeates into the positive active layer through the porous current-collecting positive layer of the positive plate to form a part or all of the positive active layer in a slurry state.
The invention has the advantages that:
the positive active layer in the invention is a stacking state of positive conductive particles, and is in a slurry state after being injected with electrolyte. The positive active layer in the accumulation state of the positive conductive particles is more convenient for compatibility assembly of electrode plates and control of consistency of the electrode plates, and avoids the requirements of slurry filling on special equipment and environment; after the pole piece was assembled into battery module, because before electrolyte injection, the inside positive pole active layer who is the state of piling up of anodal conductive particle still of pole piece, the battery just annotates liquid when using and forms thick liquids and activate the battery simultaneously, consequently still be convenient for battery module's deposit and transportation have application prospect in large-scale energy storage power station and military and civilian deposit power.
Drawings
Fig. 1 is a schematic structural diagram of a positive plate of a lithium paste battery in an embodiment of the invention, wherein 101 — an insulating frame; 102-a porous current collecting positive electrode layer; 103-positive active layer;
fig. 2 is a schematic structural diagram of a positive plate of a lithium paste battery according to a second embodiment of the present invention, wherein 204 — a second positive active layer; 205-leak resistant organic porous layer; 206 — first positive active layer; 207 — an interface improving layer;
fig. 3 is an overall schematic view of the positive plate of the lithium paste battery of the present invention, 301 — the positive tab;
fig. 4 is a schematic view of turning a slice in the process for preparing a positive plate of a lithium paste battery, wherein 401 is a turning line; 402-slicing line; 403 — a slicing unit;
fig. 5 is a schematic structural view of a lithium paste battery of the present invention, wherein 5 — a positive electrode tab; 6, isolating the cavity; and 7, negative plate.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example one
The embodiment provides a positive plate of a lithium slurry battery, which comprises a porous current collecting positive layer 102, a positive active layer 103 and an insulating sealing frame 101 positioned at the periphery of the porous current collecting positive layer and the positive active layer. In this embodiment, the porous current collecting positive electrode layer 102 is an aluminum mesh, the thickness is 2000 μm, the porosity of the through hole is 50%, and the pore diameter is 2 mm. The positive active material, the conductive agent and the binder in the positive active layer 103 are uniformly mixed according to the mass ratio of 45:50:5, wherein the positive active material is lithium iron phosphate, the conductive agent is conductive carbon black, the binder is polyvinylidene fluoride, and the thickness of the positive active layer is 10 mm.
Example two
The embodiment provides a positive plate of a lithium slurry battery, which comprises a porous current collecting positive layer 102, a first positive active layer 206, a second positive active layer 204 and an insulating sealing frame 101 positioned at the periphery of the porous current collecting positive layer and the positive active layer. In this example, the interface improvement layer 207 is coated on the grid of the porous current collecting positive electrode layer, and in this example, a leak-proof organic porous layer 205 is provided in the two porous current collecting positive electrode layers for leak-proof.
In this example, the porous current-collecting positive electrode layer was made of stainless steel mesh with a thickness of 0.01 μm, a through-hole porosity of 90%, and a pore diameter of 0.005 mm. The interface improvement layer comprises a conductive agent and a binder, wherein the mass ratio of the binder to the conductive agent is 20: 80, wherein the conductive agent is carbon black, and the binder is polyvinylidene fluoride.
The interface improvement layer is a thin layer coated on the grid of the porous current-collecting positive electrode layer, can improve the interface performance of the porous current-collecting positive electrode layer and reduce the interface resistance between the porous current-collecting positive electrode layer and the positive electrode active layer, and is compounded with the porous current-collecting positive electrode layer through spraying.
In this embodiment, the porous current collecting positive electrode layer has a large pore size, and when the interface improving layer 207 is combined with the grid of the porous current collecting positive electrode layer and the first positive active layer 206 falls into the pore size of the porous current collecting positive electrode layer, material leakage occurs, so in this embodiment, a layer of leakage-proof organic porous layer 205 is combined between two porous current collecting positive electrode layers by rolling, and the leakage-proof organic porous layer is made of a polyester non-woven fabric.
In this embodiment, a part of the first positive electrode active layer 206 is filled in the meshes of the porous positive electrode current collecting layer, and the positive electrode active material, the conductive agent and the binder in the first positive electrode active layer are uniformly mixed according to a mass ratio of 90:5: 5; the second positive electrode active layer 204 is in close contact with the first positive electrode active layer, and the positive electrode conductive particles in the second positive electrode active layer contain only a conductive agent. In this embodiment, the positive electrode active material is lithium cobaltate, the conductive agent is graphene, the binder is a mixture of styrene butadiene rubber and carboxymethyl cellulose, and the total thickness of the first positive electrode active layer and the second positive electrode active layer is 3 mm.
EXAMPLE III
The embodiment provides a lithium slurry battery positive plate, which is different from the second embodiment in that positive conductive particles in a second positive active layer contain a conductive agent and a binder in a mass ratio of 97:3, wherein the conductive agent is a mixture of ketjen black and carbon nanotubes, and the binder is polyacrylonitrile. Meanwhile, a thin conductive layer is coated on the surface of the second positive active layer, and the conductive layer is partially or completely filled in the pores of the second positive active layer in a suction filtration mode, so that particles in the positive active layer are better ensured to be in a conductive network all the time. In this embodiment, the conductive layer only contains a conductive agent, wherein the conductive agent is carbon fiber.
Example four
The invention provides a preparation process of the lithium slurry battery positive plate, which comprises the following steps:
(1) and introducing the porous current-collecting positive electrode layer into a spraying cleaning chamber and an ultrasonic cleaning tank, spraying and ultrasonically cleaning by using a cleaning solvent, and introducing a drying channel for hot air drying, wherein the cleaning solvent can be one or more of deionized water, ethanol, acetone, dilute hydrochloric acid and dilute sodium hydroxide solution according to different porous current-collecting positive electrode layer materials.
(2) Weighing and uniformly mixing the positive active material, the conductive agent and the binder according to the mass ratio of 85:12:3 to obtain positive active layer slurry;
(3) uniformly and intermittently coating the slurry of the positive electrode active layer obtained in the step (2) on one side of the porous current collecting positive electrode layer by a coating machine, wherein the coating thickness is 0.05 mm;
(4) and turning over the slices: slicing two adjacent coating areas in the step (3) as a slicing unit 403 along a slicing line 402, folding the sliced unit along a folding line 401 to form quasi-pole pieces, wherein the uncoated surface of the porous current collecting positive electrode layer of each quasi-pole piece faces outwards;
(5) and pressurizing and drying: properly pressurizing the upper and lower surfaces of the quasi-pole piece by using a clamping plate, setting the quasi-pole piece in a high-temperature oven for drying at the drying temperature of 100 ℃ for 24 hours under the pressure of 0.01MPa, naturally cooling the dried quasi-pole piece in the oven to the room temperature, and enabling positive conductive particles in a positive active layer in the dried quasi-pole piece to be in a stacking state;
(6) edge packaging: and welding and packaging the four sides of the quasi-pole piece by using an ultrasonic welding machine, and adding an insulating frame by hot pressing to obtain the positive pole piece.
EXAMPLE five
The invention provides a preparation process of the lithium slurry battery positive plate, which comprises the following steps:
(1) introducing the porous current-collecting positive electrode layer into a spraying cleaning chamber and an ultrasonic cleaning tank, spraying and ultrasonically cleaning by using a cleaning solvent, and introducing a drying channel for hot air drying, wherein the cleaning solvent can be one or more of deionized water, ethanol, acetone, dilute hydrochloric acid and dilute sodium hydroxide solution according to different porous current-collecting positive electrode layer materials;
(2) placing a layer of leakage-proof organic porous layer between the two porous current-collecting positive electrode layers, and rolling and compounding the layers;
(3) and preparing interface improvement layer slurry, wherein the mass ratio of the binder to the conductive agent is 5: 95, coating the interface improving layer slurry on one side of the porous current collecting positive electrode layer, wherein the coating layer is positioned at the grid of the porous current collecting positive electrode layer;
(4) preparing positive active layer slurry, weighing and uniformly mixing the positive active material, the conductive agent and the binder according to the mass ratio of 59:31:10 to obtain first positive active layer slurry; weighing and uniformly mixing a conductive agent to serve as a second positive electrode active layer;
(5) uniformly and intermittently coating the slurry of the first positive electrode active layer obtained in the step (4) on one side of the porous current collecting positive electrode layer through a coating machine, wherein the slurry is tightly contacted with the interface improvement layer, the coating thickness is 0.5mm, and the first positive electrode active layer is partially filled in meshes of the porous current collecting positive electrode layer; uniformly and intermittently coating the second positive electrode active layer slurry obtained in the step (4) on the surface of the first positive electrode active layer by a coating machine;
(6) and turning over the slices: slicing two adjacent coating areas in the step (3) as a unit, folding the sliced unit from the middle to form quasi-pole pieces, wherein the uncoated surface of the porous current collecting positive electrode layer of each quasi-pole piece faces outwards;
(7) and pressurizing and drying: properly pressurizing the upper and lower surfaces of the quasi-pole piece by using a clamping plate, setting the quasi-pole piece in a high-temperature oven for drying at 140 ℃ for 2h, naturally cooling the dried quasi-pole piece in the oven to room temperature, and drying the positive active layer in the dried quasi-pole piece to be in a dry state;
(8) and edge packaging: and welding and packaging the four sides of the quasi-pole piece by using an ultrasonic welding machine, and adding an insulating frame by hot pressing to obtain the positive pole piece.
Example 6
The embodiment provides a lithium slurry battery, which comprises a battery core, wherein the battery core comprises a plurality of positive plates 5 and negative plates 7 which are alternately arranged, the distance between each positive plate 5 and each negative plate 7 is 0.05-1 mm, an isolation cavity 6 is formed by the distance, and electrolyte is filled in the isolation cavity 6; the positive electrode 5 piece comprises a porous current collecting positive electrode layer, a positive electrode active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current collecting positive electrode layer and the positive electrode active layer, wherein the positive electrode active layer is positioned between the two porous current collecting positive electrode layers; the positive electrode active layer contains part or all of non-adhesive fixed positive electrode conductive particles, and the positive electrode conductive particles are conductive agents, or the positive electrode conductive particles are compounds or mixtures of positive electrode active materials and the conductive agents; the negative plate comprises a porous current-collecting negative layer, a negative active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current-collecting negative layer and the negative active layer, wherein the negative active layer is positioned between the two porous current-collecting negative layers; the negative electrode active layer is a metal lithium sheet, or the negative electrode active layer contains part or all of non-bonding fixed negative electrode conductive particles, and the negative electrode conductive particles are a compound or a mixture of a lithium-embeddable negative electrode active material and a conductive agent; the lithium-embeddable negative electrode active material comprises one or more of graphite, hard carbon, soft carbon, tin-based alloy, aluminum-based alloy, lithium titanate or silicon-based material.
And injecting electrolyte into the battery cell after the battery cell is assembled, dehumidified and vacuumized, wherein the electrolyte enters the isolation cavity and then permeates into the positive active layer through the porous current-collecting positive layer of the positive plate to form the positive active layer with part or all of the positive active layer in a slurry state.
The specific embodiments of the present invention are not intended to be limiting of the invention. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (14)
1. The utility model provides a lithium thick liquids battery positive plate, lithium thick liquids battery positive plate includes porous mass flow positive pole layer, anodal active layer and is located porous mass flow positive pole layer with anodal active layer insulating seal frame all around, wherein anodal active layer is located two-layer between the porous mass flow positive pole layer, its characterized in that: the positive electrode active layer contains part or all of non-adhesive fixed positive electrode conductive particles, the non-adhesive fixed positive electrode conductive particles are conductive agents, or the non-adhesive fixed positive electrode conductive particles are compounds or mixtures of positive electrode active materials and the conductive agents; the positive active layer is in a dry accumulation state of positive conductive particles, the dry accumulation state of the positive conductive particles comprises powder accumulation, tabletting or pressed blocks, and the porosity of the accumulation state is more than 5% and less than 60%.
2. The positive electrode sheet for a lithium paste battery according to claim 1, wherein: the positive electrode active layer comprises the positive electrode conductive particles and a binder, or the positive electrode active layer only comprises the positive electrode conductive particles, the thickness of the positive electrode active layer is 0.5-10 mm, the average particle size of the positive electrode conductive particles is 0.05-500 μm, the positive electrode conductive particles are a compound or mixture of the positive electrode active material and the conductive agent, and the mass ratio of the positive electrode active material to the conductive agent is 20-98: 80-2, and the mass ratio of the binder is not more than 10%.
3. The positive electrode sheet for a lithium paste battery according to claim 1, wherein: the positive electrode active layer comprises a first positive electrode active layer and a second positive electrode active layer, the thickness of the positive electrode active layer is 0.5-10 mm, and the thickness of the first positive electrode active layer is not less than 0.05mm and not more than 10 mm; the positive conductive particles in the first positive active layer are partially or completely positioned on the surface or in meshes of the porous current collecting positive layer, and the positive active material in the first positive active layer is as follows: conductive agent: the binder is 59-98 by mass: 1-40: 1-10, uniformly mixing; the second positive electrode active layer is in close contact with the first positive electrode active layer and comprises non-adhesive fixed positive electrode conductive particles; the average particle diameter of the positive conductive particles in the first positive active layer and the second positive active layer is 0.05-500 mu m.
4. The positive electrode sheet for a lithium paste battery according to claim 1, wherein: the positive active material of the positive active layer is one or more of lithium iron phosphate, lithium manganese phosphate, lithium silicate, lithium iron silicate, sulfate compounds, sulfur-carbon compounds, elemental sulfur, titanium sulfur compounds, molybdenum sulfur compounds, iron sulfur compounds, doped lithium manganese oxides, lithium cobalt oxides, lithium titanium oxides, lithium vanadium oxides, lithium nickel manganese oxides, lithium nickel cobalt aluminum oxides, lithium nickel cobalt manganese oxides and lithium iron nickel manganese oxides.
5. The positive electrode sheet for a lithium paste battery according to claim 1, wherein: the porous current-collecting positive electrode layer is an electronic conducting layer with a through hole structure and a thickness of 0.01-2000 mu m, the porosity of the through hole is 10-90%, and the aperture range is 0.005-2 mm;
the porous current-collecting positive electrode layer is a metal conducting layer, the metal conducting layer is a metal net, meshes of the metal conducting layer are polygons, or the metal conducting layer is a porous foam metal layer with a porous structure, or the metal conducting layer is formed by mechanically stamping or chemically corroding a metal plate or a metal foil; the metal conducting layer is made of aluminum, alloy aluminum, stainless steel, silver, tin or titanium;
or the porous current-collecting positive electrode layer is made of carbon fiber conductive cloth or conductive cloth mixed by metal wires and organic fiber wires, and the metal wires are made of copper, nickel or titanium;
or the porous current-collecting positive electrode layer is a metal conducting layer, conducting cloth, a porous organic material or a microporous inorganic non-metallic material, the surface of the porous organic material is coated with a conducting coating or plated with a metal film, the porous organic material comprises natural cotton-flax, terylene, aramid fiber, nylon, polypropylene, polyethylene and polytetrafluoroethylene, the microporous inorganic non-metallic material comprises glass fiber non-woven fabrics and ceramic fiber paper, and the conducting coating or the metal film is made of aluminum, alloy aluminum, stainless steel or silver;
or the porous current-collecting positive electrode layer is a composite layer of a metal conducting layer, conducting cloth, an inorganic non-metal material, a metal conducting layer with a conducting coating or a metal film coated on the surface, conducting cloth, an inorganic non-metal material, a porous organic material and a polymer electrolyte, and the polymer electrolyte is a gel polymer electrolyte composite material formed by compounding a polymer matrix, a liquid organic plasticizer and lithium salt;
or the porous current collecting positive electrode layer is a combination of any two or more of the above.
6. The positive electrode sheet for a lithium paste battery according to claim 5, wherein: the interface improvement layer is compounded at the grid of the porous afflux positive electrode layer by one or more modes of vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, mechanical pressing, printing or ink-jet printing; the material of the interface improvement layer comprises a conductive agent and a binder, wherein the mass ratio of the binder to the conductive agent is (0.5-20): 99.5 to 80, or the interface improving layer comprises only a conductive agent.
7. The positive electrode sheet for a lithium paste battery according to claim 5, wherein: the porous current collecting positive electrode layer further comprises a leakage-proof organic porous layer compounded on one side or two sides of the porous current collecting positive electrode layer, or the leakage-proof organic porous layer can be arranged between the two layers or the multi-layer structure of the porous current collecting positive electrode layer when the porous current collecting positive electrode layer has the two-layer or multi-layer structure; the material of the leakproof organic porous layer is carbon fiber conductive cloth, conductive cloth mixed by metal wires and organic fiber wires, or fine mesh cloth of natural cotton and linen, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene, glass fiber non-woven fabric or ceramic fiber paper; or the surfaces of the leakage-proof organic porous layer, the fine mesh cloth, the glass fiber non-woven fabric and the ceramic fiber paper are coated with conductive coatings or are plated with metal films, so that the leakage-proof organic porous layer and the porous current collecting positive electrode layer jointly play a current collecting role; and the average pore diameter and the thickness of the leakproof organic porous layer are both smaller than those of the porous current collecting positive electrode layer, the pore diameter of the leakproof organic porous layer is 10-800 mu m, the thickness is 0.01-1000 mu m, and the porosity of a through hole is 10-90%.
8. The positive electrode sheet for lithium paste batteries according to claim 2, 3 or 6, wherein: the conductive agent is one or more of graphene, carbon nano tubes, carbon fibers, amorphous carbon or metal conductive particles; the binder is a polymer material which has a wide potential window and is stable to positive and negative electrode active materials and electrolyte, and the polymer material is one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyterephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene-butadiene rubber, sodium carboxymethylcellulose, polyacetylene, polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polyterenylene and derivatives thereof, polyterephthalate and derivatives thereof, and polyfluorene and derivatives thereof.
9. A process for preparing a positive plate of a lithium slurry battery according to any one of claims 1 to 8, wherein the positive active layer is positioned between two porous current collecting positive layers, and the positive active layer in the prepared positive plate of the lithium slurry battery contains part or all of non-adhesive fixed positive conductive particles, and the process comprises the following steps:
(1) raw material pretreatment: spraying and ultrasonically cleaning the porous current-collecting positive electrode layer by using a cleaning solvent, and drying for later use; drying the required conductive agent, the positive electrode active material and the binder for later use; wherein the drying temperature of the binder is lower than the softening point of the binder material by 20 ℃, the drying time is not more than 2 hours, the drying temperature of the conductive agent and the positive active material is 100-250 ℃, and the drying time is 2-4 hours;
(2) preparing a positive active layer material: weighing the positive active material, the conductive agent and the binder required by the porous positive material layer according to the proportion, and uniformly stirring and mixing the positive active material, the conductive agent and the binder to obtain a positive active material layer;
(3) coating a positive electrode active layer: uniformly and intermittently coating the positive electrode active layer material obtained in the step (2) on one side of the porous current collecting positive electrode layer through a coating machine so as to form a plurality of coating areas;
(4) and turning over the slices: slicing two adjacent coating areas in the step (3) as a unit, folding the sliced unit from the middle to form quasi-pole pieces, wherein the uncoated surface of the porous current collecting positive electrode layer of each quasi-pole piece faces outwards;
(5) and pressurizing and drying: pressurizing the upper surface and the lower surface of the quasi-pole piece by using a clamping plate, then placing the quasi-pole piece in a high-temperature oven for drying at the drying temperature of 100-140 ℃ for 2-24 h, naturally cooling the dried quasi-pole piece in the oven to room temperature, wherein a positive active layer in the dried quasi-pole piece contains part or all of non-adhesive fixed positive conductive particles;
(6) edge packaging: and welding and packaging the four sides of the quasi-pole piece by using an ultrasonic welding machine, and adding an insulating frame by hot pressing to obtain the positive pole piece.
10. The process for preparing the positive plate of the lithium slurry battery according to claim 9, wherein in the step (1), after the porous current collecting positive electrode layer is cleaned and dried, the interface improvement layer is compounded at the grid of the porous current collecting positive electrode layer by one or more of vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, mechanical pressing, printing or ink-jet printing.
11. The process for preparing the positive plate of the lithium slurry battery according to claim 9, wherein in the step (1), after the porous current collecting positive electrode layer is cleaned and dried, the leakproof organic porous layer is compounded on one side or two sides of the porous current collecting positive electrode layer or in the middle of the double-layer or multi-layer structure of the porous current collecting positive electrode layer by means of mechanical pressing, bonding and coating.
12. The process for preparing the positive plate of the lithium slurry battery according to claim 9, wherein in the step (2), the positive active layer material comprises a first positive active layer and a second positive active layer, wherein the first positive active layer is in close contact with the porous current-collecting positive layer by one or more of bonding, mechanical pressing and coating, and the second positive active layer is in contact with the first positive active layer by one or more of vacuum evaporation, magnetron sputtering, plasma deposition, bonding, mechanical pressing, printing, inkjet printing and coating.
13. A lithium paste battery comprising the positive electrode sheet according to any one of claims 1 to 8 or the positive electrode sheet obtained by the production process according to any one of claims 9 to 12, comprising a cell, characterized in that: the battery cell comprises a plurality of positive plates and negative plates which are alternately arranged, the distance between the positive plates and the negative plates is 0.05-1 mm, and the distance forms an isolation cavity;
the negative plate comprises a porous current-collecting negative layer, a negative active layer and an insulating sealing frame fixedly sealed at the periphery of the porous current-collecting negative layer and the negative active layer, wherein the negative active layer is positioned between the two porous current-collecting negative layers; the negative electrode active layer is a metal lithium sheet, or the negative electrode active layer contains part or all of non-bonding fixed negative electrode conductive particles, and the negative electrode conductive particles are a compound or a mixture of a lithium-embeddable negative electrode active material and a conductive agent; the lithium-embeddable negative electrode active material comprises one or more of graphite, hard carbon, soft carbon, tin-based alloy, aluminum-based alloy, lithium titanate or silicon-based material.
14. The lithium paste battery of claim 13, wherein the battery cell is assembled, dehumidified, and evacuated prior to electrolyte injection, the electrolyte enters the separator chamber and then permeates into the positive active layer through the porous current collecting positive layer of the positive plate to form a partially or fully slurry positive active layer.
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| CN201610620726.4A CN107681114B (en) | 2016-08-01 | 2016-08-01 | Positive plate, preparation process and lithium slurry battery containing positive plate |
| PCT/CN2017/075925 WO2017152836A1 (en) | 2016-03-08 | 2017-03-08 | Cell for lithium paste battery, and lithium paste battery module |
| US16/082,838 US10868337B2 (en) | 2016-03-08 | 2017-03-08 | Cell-core for lithium slurry battery, and lithium slurry battery module |
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| CN113130848B (en) * | 2018-03-13 | 2022-11-11 | 宁德新能源科技有限公司 | Electrode and lithium ion battery |
| CN109037587B (en) * | 2018-08-07 | 2020-11-17 | 桑顿新能源科技有限公司 | Electrode and preparation method thereof |
| CN113410469B (en) * | 2018-10-31 | 2022-06-03 | 宁德时代新能源科技股份有限公司 | Negative pole piece, secondary battery and electric automobile |
| CN109741968B (en) * | 2018-12-29 | 2020-12-22 | 西安西电电力电容器有限责任公司 | Hybrid super capacitor battery based on nano-modified composite material electrode and manufacturing method thereof |
| CN109817910A (en) * | 2019-01-09 | 2019-05-28 | 蜂巢能源科技有限公司 | Positive electrode and preparation method thereof for solid lithium ion battery |
| CN112310488B (en) * | 2019-07-24 | 2021-10-12 | 北京好风光储能技术有限公司 | Preparation method and equipment of battery cell of coiled lithium slurry battery and battery cell |
| CN110797507B (en) * | 2019-09-16 | 2021-02-23 | 中银（宁波）电池有限公司 | Preparation process of lithium battery anode and lithium battery comprising same |
| CN111193074B (en) * | 2019-12-11 | 2021-06-29 | 国网经济技术研究院有限公司 | Detachable lithium slurry battery's compound unit and contain its lithium slurry battery |
| CN111725482B (en) * | 2020-07-27 | 2023-07-18 | 江西星盈科技有限公司 | Thick electrode and battery |
| CN113036149B (en) * | 2021-03-03 | 2023-07-28 | 大连中比动力电池有限公司 | Dry-method positive electrode plate of lithium ion secondary battery and preparation method thereof |
| CN114639798B (en) * | 2022-03-31 | 2024-05-07 | 珠海冠宇电池股份有限公司 | Pole piece, battery core and battery |
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