CN112133923A - Positive electrode material layer suitable for semi-solid battery, preparation method of positive electrode material layer, positive plate and semi-solid battery - Google Patents

Positive electrode material layer suitable for semi-solid battery, preparation method of positive electrode material layer, positive plate and semi-solid battery Download PDF

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CN112133923A
CN112133923A CN202011069813.8A CN202011069813A CN112133923A CN 112133923 A CN112133923 A CN 112133923A CN 202011069813 A CN202011069813 A CN 202011069813A CN 112133923 A CN112133923 A CN 112133923A
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positive electrode
solid electrolyte
material layer
electrode material
equal
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CN112133923B (en
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马忠龙
郑晓醒
秦士林
赵晓宁
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a positive electrode material layer suitable for a semi-solid battery, a preparation method of the positive electrode material layer, a positive plate and the semi-solid battery. The positive electrode material layer includes: a network structure formed by overlapping polymer fibers with each other, and a positive electrode active material, a solid electrolyte and a conductive agent dispersed and bonded in the network structure, wherein the solid electrolyte comprises an oxide solid electrolyte and a polymer solid electrolyte. In the positive electrode material layer, the polymer fibers are used as a binder to construct a network structure, so that the uniform dispersion of a positive electrode active substance, a solid electrolyte and a conductive agent is facilitated, the oxide solid electrolyte and the polymer solid electrolyte have good ion conductivity, the ion conductivity of the positive electrode sheet is increased by dispersing the oxide solid electrolyte and the polymer solid electrolyte in the network structure, the using amount of electrolyte is reduced, the semi-solid battery is assembled, and the safety performance of the battery is improved.

Description

Positive electrode material layer suitable for semi-solid battery, preparation method of positive electrode material layer, positive plate and semi-solid battery
Technical Field
The invention relates to the technical field of batteries, and relates to a positive electrode material layer of a semi-solid battery, a preparation method of the positive electrode material layer, a positive plate and the semi-solid battery.
Background
With the rapid development of renewable energy sources such as hydropower, solar energy, wind energy, biomass energy, geothermal energy and the like, the renewable energy source is coming into a new era that the traditional energy sources and the renewable energy sources are integrated together, and particularly with increasingly deep energy-saving and environment-friendly concepts, the energy structure is promoted to be continuously developed towards the sustainable and clean directions.
In recent years, people have been dedicated to the development of new energy automobiles, and the main problem which hinders the popularization of new energy automobiles at present is the cost problem. The current move from the research of new materials to the development of advanced battery systems is towards a goal, namely to reduce costs. Although the wet coating process adopted by the preparation of the anode and the cathode in the battery is continuously optimized, the process and equipment reach a mature stage, the complex processes of drying, solvent recovery and retreatment and the like are required after the wet coating process, the cost of manpower and material resources is increased, and the manufacturing cost of the battery is difficult to reduce.
In addition, with the mass popularization of electronic products, the lithium battery used as a power source of the electronic products is increasingly gaining attention due to the advantages of light weight, small size, high working voltage, high energy density, large output power, high charging efficiency, no memory effect and the like. Therefore, the requirements for the safety and electrochemical performance of lithium batteries are inevitably higher and higher, and therefore, the improvement of the safety performance and electrochemical performance of the batteries is one of the main targets of the future lithium ion battery research. Currently commercially available lithium ion batteries are liquid electrolyte batteries. The liquid electrolyte is generally composed of a lithium salt, an organic solvent and an additive, and is in a liquid state that is easily flowable at room temperature. After the battery is subjected to a strong impact or the inside of the battery swells, the battery package is easily broken and the liquid electrolyte leaks out. Since the liquid electrolyte contains a large amount of flammable and explosive organic solvents, great potential safety hazards are generated.
In order to reduce the environmental pollution caused by battery manufacturing, reduce the cost, and improve the safety performance of the battery, it is necessary to provide a positive electrode material layer to meet the high demand of people for new energy batteries.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a positive electrode material layer suitable for a semi-solid battery, a method for preparing the same, a positive electrode sheet, and a semi-solid battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode material layer of a semi-solid state battery, the positive electrode material layer including: the lithium ion secondary battery comprises a network structure formed by overlapping polymer fibers, and a positive electrode active material, a solid electrolyte and a conductive agent which are dispersed and bonded in the network structure, wherein the solid electrolyte comprises an oxide solid electrolyte and a polymer solid electrolyte, the polymer solid electrolyte is a mixture of a high-voltage-resistant polymer and a lithium salt, and the high-voltage-resistant polymer comprises at least one of Polyimide (PI), polyvinylidene fluoride (PVDF) and Polyacrylonitrile (PAN).
In the positive electrode material layer, on one hand, the polymer fibers are used as the binder to construct a network structure, so that the uniform dispersion of the positive electrode active substance, the solid electrolyte and the conductive agent is facilitated, the oxide solid electrolyte and the polymer solid electrolyte have good ion conductivity, the ion conductivity of the positive electrode sheet is increased by dispersing the oxide solid electrolyte and the polymer solid electrolyte in the network structure, the using amount of the electrolyte is reduced, the semi-solid battery is assembled, and the safety performance of the battery is improved. On the other hand, the high-voltage resistant polymer electrolyte provides ion conduction capability, avoids decomposition under high voltage (such as 3.9-4.5V) in the charging and discharging process, has good electrolyte wettability, has swelling effect, further reduces the electrolyte consumption on the premise of good electrolyte wettability of the oxide solid electrolyte, and improves the safety of the battery.
The high voltage resistant polymer in the present invention includes, but is not limited to, the above listed kinds, and other polymers having high voltage resistant characteristics and good swelling property in an electrolyte, which are commonly used in the art, are also suitable for the present invention.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the oxide solid electrolyte comprises Li7-x'La3Zr2-x'Tax'O12(LLZTO)、Li7-2y'La3Zr2-y'Wy”O12(LLZWTO)、Li7-z'La3Zr2-z'Nbz'O12(LLZNO)、Li7La3Zr2O12(LLZO)、Li1+m'Alm'Ti2-m'(PO4)3(LATP) and Li1+n'Aln'Ge2-n'(PO4)3(LAGP) of 0.2<x'<2，0.2<y'<2，0.2<z'<2，0.2<m'<2，0.2<n'<2。
Preferably, the high pressure resistant polymer further comprises at least one of polyethylene oxide, polyvinyl chloride, polymethyl methacrylate, polyacrylic acid, polystyrene and polyethylene oxide-polystyrene copolymer.
Preferably, the lithium salt includes at least one of lithium bistrifluoromethylsulfonate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, lithium bistrifluorosulfonimide.
Preferably, the network-like structure is formed by drawing the fiberizable polymer under shear to form fibers and overlapping each other during the autoclave process.
Preferably, the polymer fiber includes at least one of Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polypropylene (PP), Polyethylene (PE), and nitrile-butadiene rubber (NBR), preferably PTFE.
The type of the positive electrode active material is not limited in the invention, and the positive electrode active material commonly used in the field is all applicable to the invention, and can be a doped positive electrode active material or an undoped positive electrode active material, and can typically but not limited by Li1+x1NiyCozMntMsO2-、LiMx2Mn2-x2O4、LiFe1-x3Mx3PO4、Li2Fe1-x4Mx4SiO4And LiFe1- x5Mx5SO4At least one of F, wherein x1 is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, t is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, 0 is more than or equal to 0 and less than or equal to 0.2, x2 is more than or equal to 0 and less than or equal to 1, x3 is more than or equal to 0 and less than or equal to 1, and M is selected from Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sn, Pb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, W.
Preferably, the positive electrode active material is LiCoO2、LiNiO2、LiFePO4、LiNi0.5Mn0.5O2、Li(NiCoMn)1/3O2、Li1.2Ni0.13Mn0.54Co0.13O2And LiMn2O4At least one of (1).
The present invention is not limited to the kind of the conductive agent, and conductive agents commonly used in the art are all applicable to the present invention, and may typically, but not limitedly, include conductive carbon materials including at least one of acetylene black, conductive carbon black (Super-P), carbon nanotubes, carbon fibers, ketjen black, graphite conductive agents, and graphene.
Preferably, the polymer fiber accounts for 1 to 30% by mass, for example, 1%, 2%, 5%, 7%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30% or the like, preferably 3 to 10% by mass, based on 100% by mass of the total mass of the positive electrode material layer.
Preferably, the positive electrode active material has a mass ratio of 25% to 98.5%, for example, 25%, 27%, 30%, 33%, 36%, 40%, 45%, 48%, 50%, 55%, 60%, 63%, 66%, 70%, 75%, 80%, 85%, 90%, 96%, 98%, or the like, preferably 67.5% to 96%, based on 100% of the total mass of the positive electrode material layer.
Preferably, the solid electrolyte accounts for 0.5-20% of the total mass of the positive electrode material layer, such as 0.5%, 1%, 2%, 4%, 6%, 10%, 15%, or 20%, and if the solid electrolyte content is less than 0.5%, the ionic conductivity of the positive electrode after the addition cannot be effectively improved, and the reduction of the electrolyte usage is not greatly facilitated; if the solid electrolyte content is higher than 20%, the content of the positive active material is lower, so that the energy density of the whole battery system is reduced, and more preferably 2% -10%.
Preferably, the high voltage resistant polymer accounts for 50% -70% of the total amount of the oxide solid electrolyte and the polymeric solid electrolyte, such as 50% \ 60%, 62%, 64%, 65%, 67%, 68% or 70%, and within this preferred range, high ionic conductivity and good liquid absorption and retention performance can be better combined.
Preferably, the conductive agent accounts for 0.5 to 5% by mass, such as 0.5%, 1%, 1.5%, 2%, 3%, 4%, or 5% by mass, and the like, and preferably 1 to 2.5% by mass, based on 100% by mass of the total positive electrode material layer.
Preferably, the thickness of the positive electrode material layer is 30um-500um, such as 1um, 3um, 5um, 8um, 12um, 15um, 20um, 25um, 30um, 35um, 40um, 45um, 50um, 55um, 60um, 65um, 70um, 75um, 78um, 82um, 85um, 90um, 100um, 120um, 135um, 150um, 170um, 200um, 225um, 260um, 300um, 350um, 400um, 450um or 500um, etc.
In a second aspect, the present invention provides a method of preparing a positive electrode material layer for a semi-solid battery according to the first aspect, the method comprising the steps of:
(1) mixing the fiberizable polymer powder, the positive active substance, the solid electrolyte and the conductive agent according to the formula amount, and then drawing the fiberizable polymer powder into fibers under the action of shearing force to obtain a mixture;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1) on a current collector until the preset thickness and the preset compaction density are reached, and obtaining the anode material layer.
The invention provides a method for preparing a positive electrode material layer by adopting a dry film-making technology, which comprises the steps of mixing fiberizable polymer powder, a positive electrode active substance, a solid electrolyte and a conductive agent under a dry condition, drawing and fiberizing the fiberizable polymer under a shearing action force, carrying out hot pressing film-forming, randomly overlapping polymer fibers converted from the fiberizable polymer in the hot pressing film-forming process to form a polymer network structure with rich pores, and uniformly dispersing and bonding the hot-pressed positive electrode active substance, the solid electrolyte and the conductive agent on the polymer network structure to obtain the positive electrode material layer.
Specifically, the dry mixing is carried out in the step (1), the fiberizable polymer powder, the positive electrode active substance, the solid electrolyte and the conductive agent powder are mixed according to a certain proportion, the fiberizable polymer powder is drawn into fibers under the action of shearing force, the dry powder with certain viscosity is prepared, the degree of drawing is not specifically limited, and the mixture is bonded into a mass shape. Step (2) hot-pressing to prepare a film, namely pressing the powder mixed by the dry method into a positive electrode material layer with a certain thickness in a certain hot-pressing mode; in the hot pressing process, the polymer fibers are mutually overlapped, extruded and moved to form a network structure, and the network structure wraps and bonds other component particles together to form a self-supporting membrane, namely the anode material layer.
The positive electrode material layer prepared by the method ensures that the positive electrode active substance, the solid electrolyte and the conductive agent are uniformly dispersed in the positive electrode material layer, is favorable for improving the ion conductivity of the positive electrode material layer and reduces the using amount of the electrolyte. And the positive electrode material layer prepared by the dry method has good ductility and strong plasticity, and the positive electrode material layer with higher compaction density can be obtained by adjusting the rolling condition, so that the energy density of the battery is improved on the premise of ensuring the wettability of the electrolyte.
The compacted density of the positive electrode material layer in the present invention is not particularly limited, and may be selected by those skilled in the art as required, and is preferably not less than 3.6g/cm3E.g. 3.6g/cm3、3.7g/cm3、3.8g/cm3、3.9g/cm3Or 4.0g/cm3And the like.
According to the invention, the anode material layer is prepared by adopting a dry method technology, no organic solvent is added in the whole process, and the solubility of the solid electrolyte (especially the polymer solid electrolyte) and the solvent is not required to be considered due to no solvent, so that the optional range of the solid electrolyte is increased, the further optimization of the battery formula is facilitated, and the battery performance is improved; in addition, the drying process is omitted, the problems of post-treatment, recovery and the like of the organic solvent are avoided, the production cost is effectively saved, and the environmental pollution is avoided.
In the present invention, the method of obtaining the preset thickness and the preset compaction density by adjusting the rolling conditions is the prior art, and those skilled in the art can refer to the method disclosed in the prior art, for example, the rolling can be repeated to achieve a higher compaction density, and the rolling can also be performed for multiple times by multiple folding to obtain a higher compaction density.
As a preferred embodiment of the method of the present invention, in the mixture of step (1), the ratio of the mass of the fiberizable polymer is 1% to 30%, for example, 1%, 2%, 5%, 7%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, or 30%, and preferably 3% to 10%.
Preferably, in the mixture of step (1), the mass ratio of the positive electrode active material is 25% to 98.5%, for example, 25%, 27%, 30%, 33%, 36%, 40%, 45%, 48%, 50%, 55%, 60%, 63%, 66%, 70%, 75%, 80%, 85%, 90%, 96% or 98%, etc., preferably 67.5% to 96%.
Preferably, the mass ratio of the solid electrolyte in the mixture in the step (1) is 0.5-20%, such as 0.5%, 1%, 2%, 4%, 6%, 10%, 15% or 20%, etc., preferably 2-10%.
Preferably, in the mixture of step (1), the conductive agent accounts for 0.5-5% by mass, such as 0.5%, 1%, 1.5%, 2%, 3%, 4%, or 5%, and preferably 1-2.5%.
Preferably, the mixing speed in step (1) is less than 1000rpm, such as 100rpm, 150rpm, 200rpm, 300rpm, 350rpm, 450rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, or the like, preferably 100rpm to 700 rpm. The advantage of drawing fibers by first mixing at a lower rotational speed and then adding a fiberizable polymer is that: the components are uniformly mixed by low-speed mixing, and then the polymer powder capable of being fiberized is added for subsequent drawing, so that the drawing sufficiency and the uniformity of the components are ensured.
Preferably, in the mixing process in the step (1), the positive electrode active material, the solid electrolyte and the conductive agent are firstly mixed, and then the polymer powder capable of being fiberized is added for secondary mixing. The uniformity of each material can be better ensured by the way of adding the materials step by step.
Preferably, the step (1) of drawing the fiberizable polymer powder under shear force to form fibers comprises: at least one of high-speed stirring, screw extrusion and air flow crushing, and a mashing machine, a high-speed dispersing machine, a twin-screw extruder, an air flow crusher, and the like may be used as the equipment.
Preferably, the manner in which the fiberizable polymer powder is drawn into fibers under the action of the shear force in step (1) is high speed agitation at a speed of > 1000rpm (e.g., 2000rpm, 3000rpm, 4000rpm, 5000rpm, 6000rpm, 7000rpm, 8000rpm, 9000rpm, 10000rpm, 12000rpm, 12500rpm, 13500rpm, 15000rpm, 16500rpm, 18000rpm, 20000rpm, 21000rpm, 22500rpm, 25000rpm, etc.). However, the present invention is not limited to the above-mentioned embodiments, and other embodiments for achieving the object of fiberization are also applicable to the present invention.
Preferably, the high speed stirring is at a speed of 8000rpm to 25000rpm, such as 8000rpm, 9000rpm, 10000rpm, 11000rpm, 12000rpm, 13000rpm, 15000rpm, 17500rpm, 18500rpm, 20000rpm, 21000rpm, 22500rpm, 23500rpm, 25000rpm, etc., preferably at a speed of 17000rpm to 21000 rpm.
Preferably, the time for mixing with high speed stirring is 2min to 2h, such as 2min, 5min, 10min, 15min, 17min, 20min, 25min, 28min, 30min, 40min, 50min, 1h, 1.1h, 1.2h, 1.3h, 1.5h, 1.8h or 2h, etc., preferably 10min to 30 min.
In the invention, the purpose of high-speed shearing is to realize uniform mixing of materials on one hand and more importantly to realize fiberization by drawing fiberizable polymers under the action of ultra-strong high-speed dispersion on the other hand. If the shearing speed is too low, on one hand, the mixing time is too long, the time cost is increased, and on the other hand, the fiberization effect is not ideal; if the shearing speed is too high, the loss of the equipment is large, the service life of the equipment is reduced, and the performance of the temperature-sensitive raw material is possibly deteriorated due to the heat generation problem.
Preferably, the high speed stirring and mixing is pulse stirring, and the gap time is 0-30min, such as 0.5min, 1min, 3min, 5min, 10min, 15min, 20min, 25min or 30 min.
The form of the hot pressing treatment in step (2) is not limited in the present invention, and for example, a roller press may be used to perform hot rolling at a certain temperature.
Preferably, the hot pressing treatment in step (2) is performed at a temperature of 25 ℃ to 300 ℃, for example, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 65 ℃, 80 ℃, 100 ℃, 115 ℃, 130 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, etc., preferably at a temperature of 60 ℃ to 250 ℃, and more preferably at a temperature of 180 ℃ to 220 ℃.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) mixing a positive active substance, a solid electrolyte and a conductive agent at a low speed of 100-800 rpm, adding a fiberizable polymer powder, continuously mixing at the low speed of the original rotating speed, performing pulse type stirring at a speed of more than or equal to 1000rpm, wherein the gap time is 0-30min and does not contain 0, and the pulse type stirring time is 2min-2h to obtain a uniformly mixed mixture, wherein in the mixture, the mass ratio of the fiberizable polymer powder is 1-30%, the mass ratio of the positive active substance is 25-98.5%, the mass ratio of the solid electrolyte is 0.5-20%, and the mass ratio of the conductive agent is 0.5-5%;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1), wherein the hot-pressing temperature is 60-250 ℃, the hot-pressing speed is 5-50 rpm, and the thickness is 30-500 um, so as to obtain the self-supporting anode material layer.
In a third aspect, the present invention provides a positive electrode sheet comprising the positive electrode material layer according to the first aspect.
Preferably, the positive electrode sheet includes a current collector and a positive electrode material layer according to any one of claims 1 to 4 on a surface of the current collector.
Preferably, the current collector comprises an aluminum foil.
The preparation method of the positive plate is not limited, and the current collector (such as aluminum foil) can be combined with the positive material layer in the hot pressing process, for example, the mixture is paved on the surface of the current collector for hot pressing, so that the positive material layer is formed and the combination of the positive material layer and the positive material layer is realized. The positive electrode material layer may be prepared according to the method of the second aspect, that is, a self-supporting positive electrode material layer is obtained, and then the positive electrode material layer and a current collector (e.g., an aluminum foil) are hot-pressed (e.g., hot-rolled by using a roller press) to achieve the combination of the positive electrode material layer and the current collector. The skilled person can select the material according to the needs, and more preferably, the self-supporting positive electrode material layer is prepared first, and then the two are compounded by hot compaction.
In a fourth aspect, the present invention provides a semi-solid battery comprising the positive electrode tab of the third aspect.
The present invention is not limited to a specific type of lithium battery, and may be any one of a lithium metal battery, a lithium ion battery, a lithium air battery, and a lithium sulfur battery, for example.
Compared with the prior art, the invention has the following beneficial effects:
in the positive electrode material layer, on one hand, the polymer fibers are used as the binder to construct a network structure, so that the uniform dispersion of the positive electrode active substance, the solid electrolyte and the conductive agent is facilitated, the oxide solid electrolyte and the polymer solid electrolyte have good ion conductivity, the ion conductivity of the positive electrode sheet is increased by dispersing the oxide solid electrolyte and the polymer solid electrolyte in the network structure, the using amount of the electrolyte is reduced, the semi-solid battery is assembled, and the safety performance of the battery is improved. On the other hand, the high-voltage resistant polymer electrolyte provides ion conduction capability, avoids decomposition under high voltage (such as 3.7-4.3V) in the charging and discharging process, has good electrolyte wettability, has swelling effect, further reduces the electrolyte consumption on the premise of good electrolyte wettability of the oxide solid electrolyte, and improves the safety of the battery. The invention provides a method for preparing a positive electrode material layer by a dry method, which is different from a method for preparing the positive electrode material layer by a liquid phase method. The anode material layer is obtained by mixing the fiberizable polymer powder, the anode active substance, the solid electrolyte and the conductive agent under the dry condition, drawing and fiberizing the fiberizable polymer under the shearing action force, and hot-pressing to form a film. The anode material layer with higher compaction density can be obtained by adjusting rolling conditions (such as repeated rolling or repeated folding and rolling), so that the energy density of the battery can be improved.
According to the dry preparation technology provided by the invention, no organic solvent is added in the whole process, and the solubility of the solid electrolyte (especially the polymer solid electrolyte) and the solvent is not required to be considered due to no addition of the solvent, so that the optional range of the solid electrolyte is increased, the further optimization of a battery formula is facilitated, and the battery performance is improved; in addition, the drying process is omitted, the problems of post-treatment, recovery and the like of the organic solvent are avoided, the production cost is effectively saved, and the environmental pollution is avoided.
The preparation method is simple in preparation process and easy to amplify, is a method suitable for industrial application, is beneficial to promoting the development of new energy industry, and has wide application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a positive electrode material layer and a preparation method thereof, wherein the method comprises the following steps:
8g of lithium nickel cobalt manganese (Li (NiCoMn))1/3O2) 0.2g of carbon nano tube, 0.3g of Lithium Lanthanum Zirconium Oxide (LLZO), 0.6g of polyimide and 0.1g of lithium bis (trifluoromethyl) sulfonate are added into a stirrer, and are stirred for 10 minutes in a low-speed (100rpm) pulse mode and mixed uniformly, then 0.8g of polytetrafluoroethylene is added, and are stirred for 10 minutes in a low-speed (100rpm) pulse mode and mixed uniformly, and are stirred for 30 minutes in a high-speed (10000rpm) pulse mode, and a fiberization process is carried out. The mixed powder is put into a roller press and hot-rolled at 150 ℃ to form a self-supporting film, namely a self-supporting positive electrode material layer.
The positive electrode material layer prepared in this example includes a network structure formed by overlapping polytetrafluoroethylene fibers, and a positive electrode active material li (nicomn) dispersed and bonded in the network structure1/3O2The conductive material comprises a solid electrolyte (consisting of an oxide solid electrolyte LLZO and a polymer solid electrolyte, wherein the polymer solid electrolyte is a mixture of polyacrylonitrile and lithium bistrifluoromethylsulfonate imide) and a conductive agent carbon nano tube. Specifically, the mass percentage of the polymer fibers is 8%, the mass percentage of the positive electrode active material is 80%, the mass percentage of the solid electrolyte is 10%, and the mass percentage of the conductive agent is 2%, based on 100% of the total mass of the positive electrode material layer. Wherein, the polyimide/(oxide solid electrolyte + polymer solid electrolyte) ═ 60 wt%/100 wt%.
The embodiment provides a positive plate, which comprises an aluminum foil and the positive electrode material layer, and is prepared by hot-pressing and compounding the positive electrode material layer on the aluminum foil.
Example 2
The embodiment provides a positive electrode material layer and a preparation method thereof, wherein the method comprises the following steps:
8.3g of lithium nickel cobalt manganese (Li (NiCoMn))1/3O2) 0.2g of carbon nano tube, 0.2g of Lithium Lanthanum Zirconium Oxide (LLZO), 0.7g of polyacrylonitrile and 0.1g of lithium bis (trifluoromethyl) sulfonate imine are added into a stirrer, and are stirred for 10 minutes in a low-speed (300rpm) pulse mode and mixed uniformly, then 0.5g of polytetrafluoroethylene is added, and are stirred for 10 minutes in a low-speed (300rpm) pulse mode and mixed uniformly in a high-speed (1600 rpm) pulse mode0rpm) was pulsed for 20 minutes, the fiberization process was performed. The mixed powder is put into a roller press and hot-rolled at 150 ℃ to form a self-supporting film, namely a self-supporting positive electrode material layer.
The positive electrode material layer prepared in this example includes a network structure formed by overlapping polytetrafluoroethylene fibers, and a positive electrode active material li (nicomn) dispersed and bonded in the network structure1/3O2The conductive material comprises a solid electrolyte (consisting of an oxide solid electrolyte LLZO and a polymer solid electrolyte, wherein the polymer solid electrolyte is a mixture of polyacrylonitrile and lithium bistrifluoromethylsulfonate imide) and a conductive agent carbon nano tube. Specifically, the mass percentage of the polymer fibers is 5%, the mass percentage of the positive electrode active material is 83%, the mass percentage of the solid electrolyte is 10%, and the mass percentage of the conductive agent is 2%, based on 100% of the total mass of the positive electrode material layer. Wherein, polyacrylonitrile/(oxide solid electrolyte + polymer solid electrolyte) ═ 70 wt%/100 wt%.
The embodiment provides a positive plate, which comprises an aluminum foil and the positive electrode material layer, and is prepared by hot-pressing and compounding the positive electrode material layer on the aluminum foil.
Example 3
The embodiment provides a positive electrode material layer and a preparation method thereof, wherein the method comprises the following steps:
8.1g of lithium nickel cobalt manganese (Li (NiCoMn))1/3O2) 0.1g of carbon nanotubes, 0.1g of Super-P, 0.25g of Li6.6La3Zr1.6Ta0.4O12Adding 0.3g of polyacrylonitrile, 0.25g of polyvinylidene fluoride and 0.1g of lithium hexafluorophosphate into a stirrer, performing low-speed (200rpm) pulse stirring for 10 minutes, uniformly mixing, then adding 0.8g of polytetrafluoroethylene, performing low-speed (200rpm) pulse stirring for 5 minutes, uniformly mixing, and performing high-speed (18000rpm) pulse stirring for 30 minutes to perform a fiberization process. The mixed powder was placed in a roller press and hot rolled at 130 ℃ to form a self-supporting film, i.e. a self-supporting positive electrode material layer.
The positive electrode material layer prepared in this embodiment includes a network structure formed by overlapping polytetrafluoroethylene fibers, and a positive electrode active material lithium cobaltate, a solid electrolyte (composed of an oxide solid electrolyte LLZTO and a polymer solid electrolyte, specifically a mixture of polyacrylonitrile, polyvinylidene fluoride and lithium hexafluorophosphate), and a conductive agent (a mixture of carbon nanotubes and Super-P in a mass ratio of 1: 1) dispersed and bonded in the network structure. Specifically, the mass ratio of the polymer fibers is 8%, the mass ratio of the positive electrode active material is 81%, the mass ratio of the solid electrolyte is 9%, and the mass ratio of the conductive agent is 2%, based on 100% of the total mass of the positive electrode material layer. Wherein, polyacrylonitrile + polyvinylidene fluoride/(oxide solid electrolyte + polymeric solid electrolyte) ═ 55 wt%/100 wt%.
The embodiment provides a positive plate, which comprises an aluminum foil and the positive electrode material layer, and is prepared by hot-pressing and compounding the positive electrode material layer on the aluminum foil.
Example 4
The difference from example 1 is that polyimide/(oxide solid electrolyte + polymeric solid electrolyte) — 20 wt%/100 wt%, the amount of solid electrolyte added, the mass ratio of LLZO to lithium bistrifluoromethylenesulfonate, and other preparation methods and conditions were the same as in example 1.
Example 5
The difference from example 1 is that the polyimide/(oxide solid electrolyte + polymeric solid electrolyte) — 75 wt%/100 wt%, the amount of solid electrolyte added, the mass ratio of LLZO to lithium bistrifluoromethylsulfonate, and other preparation methods and conditions were the same as example 1.
Example 6
The difference from example 1 is that the solid electrolyte content is 0.5% by mass, the polymer fiber content is 8% by mass, the conductive agent content is 2% by mass, and the negative electrode active material content is 89.5% by mass, and other preparation methods and conditions are the same as example 1.
Example 7
The difference from example 1 is that the solid electrolyte mass ratio is 20%, the polymer fiber mass ratio is 8%, the conductive agent mass ratio is 2%, and the negative electrode active material mass ratio is 70%, and other preparation methods and conditions are the same as example 1.
Example 8
The difference from example 1 is that all the materials were directly mixed and subjected to high-speed pulse stirring without low-speed pulse stirring, and other preparation methods and conditions were the same as example 1.
Comparative example 1
The comparative example is different from example 1 in that the types and contents of active materials are the same as those of example 1, the types and contents of conductive agents are the same as those of example 1, polyvinylidene fluoride (PVDF-HSV900) is used as a binder, N-methyl pyrrolidone is used as a solvent, and processes such as homogenizing, wet coating, drying, rolling and the like are performed to form the positive plate.
Comparative example 2
The difference from example 1 is that the kind of the solid electrolyte is only lithium lanthanum zirconium oxide, and the additive amount of the solid electrolyte and other preparation methods and conditions are the same as those of example 1.
Comparative example 3
The difference from example 1 is that the kind of the solid electrolyte is only a polymer solid electrolyte, and the amount of the added solid electrolyte, the mass ratio of the polyimide and lithium bistrifluoromethylsulfonate, and other preparation methods and conditions are the same as those of example 1.
And (3) testing:
the positive plates of the above examples and comparative examples were assembled to discharge lithium, the separator was a PE film, and the electrolyte was LiPF6(concentration 1M in electrolyte) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with a volume ratio of 1:1:1, the addition amount of the electrolyte is half of the volume of the liquid battery (1g/Ah), and charging and discharging are carried out at 0.1C, and the test results are shown in Table 1.
TABLE 1
Figure BDA0002713827530000151
Figure BDA0002713827530000161
As can be seen from the above table, the positive electrode material layer of the present invention has the advantages of high energy density and effective reduction of the amount of the electrolyte.
It is understood from the comparison of examples 4 to 5 with example 1 that the battery capacity is reduced when the ratio of the high-pressure resistant polymer to the oxide electrolyte is not within the maximum range, and that the electrochemical performance of the battery can be improved by combining high ionic conductivity and good liquid-absorbing and liquid-retaining properties when the ratio is within the preferred range.
It can be seen from the comparison between examples 6 to 7 and example 1 that the addition amount of the solid electrolyte is too low, so that the ionic conductivity of the electrode sheet itself is not improved, and the ionic conductivity of the electrode sheet is reduced under the condition of less addition amount of the electrolyte, thereby affecting the capacity exertion of the electrode sheet. When the solid electrolyte is added in an excessive amount, the content of active substances is obviously reduced, so that the energy density of the whole pole piece is seriously reduced.
As can be seen from the comparison between the example 8 and the example 1, the positive plate which is not subjected to low-speed mixing has low initial efficiency, and uneven mixing is caused by direct fiberization of polytetrafluoroethylene due to direct high-speed stirring, so that the capacity exertion of the plate is influenced.
Compared with the embodiment 1, the positive plate has higher first effect and higher compaction density under the condition of consistent electrolyte dosage.
Comparing comparative examples 2 to 3 with example 1, it can be seen that when the solid electrolyte is of a single type or the content ratio of the two is not within the optimal range, the ion conductivity and the liquid absorption capacity of the electrode sheet do not reach the optimal values, so that the capacity of the electrode sheet is reduced.
In conclusion, the invention can effectively reduce the consumption of the electrolyte in the battery, improve the safety performance of the battery and has advantages in volume energy density.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A positive electrode material layer of a semi-solid state battery, comprising: the lithium ion battery comprises a network structure formed by mutually lapping polymer fibers, and a positive electrode active material, a solid electrolyte and a conductive agent which are dispersed and bonded in the network structure, wherein the solid electrolyte comprises an oxide solid electrolyte and a polymer solid electrolyte, the polymer solid electrolyte is a mixture of a high-voltage-resistant polymer and a lithium salt, and the high-voltage-resistant polymer comprises at least one of polyimide PI, polyvinylidene fluoride PVDF and polyacrylonitrile PAN.
2. The positive electrode material layer of claim 1, wherein the oxide solid electrolyte comprises Li7-x'La3Zr2-x'Tax'O12、Li7-2y'La3Zr2-y'Wy”O12、Li7-z'La3Zr2-z'Nbz'O12、Li7La3Zr2O12、Li1+m'Alm'Ti2-m'(PO4)3And Li1+n'Aln'Ge2-n'(PO4)3At least one of (1), wherein, 0.2<x'<2，0.2<y'<2，0.2<z'<2，0.2<m'<2，0.2<n'<2；
Preferably, the high pressure resistant polymer also comprises at least one of polyethylene oxide, polyvinyl chloride, polymethyl methacrylate, polyacrylic acid, polystyrene and polyethylene oxide-polystyrene copolymer;
preferably, the lithium salt includes at least one of lithium bistrifluoromethylsulfonate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate, lithium bistrifluorosulfonimide.
3. The positive electrode material layer according to claim 1 or 2, wherein the network-like structure is formed by drawing a fiberizable polymer under a shearing force to form fibers, and overlapping each other during a hot pressing process;
preferably, the polymer fiber includes at least one of Polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polypropylene (PP), Polyethylene (PE), and nitrile-butadiene rubber (NBR), preferably PTFE;
preferably, the positive electrode active material includes Li1+x1NiyCozMntMsO2-、LiMx2Mn2-x2O4、LiFe1-x3Mx3PO4、Li2Fe1-x4Mx4SiO4And LiFe1-x5Mx5SO4At least one of F, wherein x1 is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, t is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, 0 is more than or equal to 0 and less than or equal to 0.2, x2 is more than or equal to 0 and less than or equal to 1, x3 is more than or equal to 0 and less than or equal to 1, and M is selected from Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sn, Pb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu;
preferably, the positive electrode active material is LiCoO2、LiNiO2、LiFePO4、LiNi0.5Mn0.5O2、Li(NiCoMn)1/3O2、Li1.2Ni0.13Mn0.54Co0.13O2And LiMn2O4At least one of;
preferably, the conductive agent includes a conductive carbon material including at least one of acetylene black, conductive carbon black, carbon nanotubes, carbon fibers, ketjen black, a graphite conductive agent, and graphene.
4. The positive electrode material layer according to any one of claims 1 to 3, wherein the polymer fiber accounts for 1 to 30% by mass, preferably 3 to 10% by mass, based on 100% by mass of the total positive electrode material layer;
preferably, the mass percentage of the positive electrode active material is 25-98.5%, preferably 67.5-96% based on 100% of the total mass of the positive electrode material layer;
preferably, the mass percentage of the solid electrolyte is 0.5-20%, preferably 2-10% based on 100% of the total mass of the positive electrode material layer;
preferably, the high-voltage resistant polymer accounts for 50-70% of the total amount of the oxide solid electrolyte and the polymeric solid electrolyte;
preferably, the mass percentage of the conductive agent is 0.5-5%, preferably 1-2.5%, based on 100% of the total mass of the positive electrode material layer;
preferably, the thickness of the positive electrode material layer is 30um-500 um.
5. A method of preparing a positive electrode material layer for a semi-solid battery according to any one of claims 1 to 4, comprising the steps of:
(1) mixing the fiberizable polymer powder, the positive active substance, the solid electrolyte and the conductive agent according to the formula amount, and then drawing the fiberizable polymer powder into fibers under the action of shearing force to obtain a mixture;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1) on a current collector until the preset thickness and the preset compaction density are reached, and obtaining the anode material layer.
6. The method according to claim 5, characterized in that in the mixture of step (1), the mass proportion of the fiberizable polymer is 1-30%, preferably 3-10%;
preferably, in the mixture in the step (1), the mass ratio of the positive electrode active substance is 25% -98.5%, and preferably 67.5% -96%;
preferably, in the mixture in the step (1), the mass ratio of the solid electrolyte is 0.5-20%, preferably 2-10%;
preferably, in the mixture in the step (1), the mass ratio of the conductive agent is 0.5-5%, preferably 1-2.5%.
7. The method according to claim 5 or 6, wherein the mixing speed of step (1) is less than 1000rpm, preferably 100rpm to 800 rpm;
preferably, in the mixing process in the step (1), the positive active material, the solid electrolyte and the conductive agent are firstly mixed, and then the polymer powder capable of being fiberized is added for secondary mixing;
preferably, the step (1) of drawing the fiberizable polymer powder under shear force to form fibers comprises: at least one of high-speed stirring, screw extrusion and airflow crushing, preferably high-speed stirring, wherein the high-speed stirring speed is more than or equal to 1000 rpm;
preferably, the high speed stirring speed is 8000rpm-25000rpm, preferably 17000rpm-21000 rpm;
preferably, the high-speed stirring and mixing time is 2min-2h, preferably 10min-30 min;
preferably, the high-speed stirring and mixing is pulse stirring, and the gap time is 0-30 min;
preferably, the hot pressing treatment of step (2) is hot rolling;
preferably, the temperature of the hot pressing treatment in the step (2) is 25-300 ℃, preferably 60-250 ℃, and further preferably 180-220 ℃.
8. A method according to any of claims 5-7, characterized in that the method comprises the steps of:
(1) mixing a positive active substance, a solid electrolyte and a conductive agent at a low speed of 100-800 rpm, adding a fiberizable polymer powder, continuously mixing at the low speed of the original rotating speed, performing pulse type stirring at a speed of more than or equal to 1000rpm, wherein the gap time is 0-30min and does not contain 0, and the pulse type stirring time is 2min-2h to obtain a uniformly mixed mixture, wherein in the mixture, the mass ratio of the fiberizable polymer powder is 1-30%, the mass ratio of the positive active substance is 25-98.5%, the mass ratio of the solid electrolyte is 0.5-20%, and the mass ratio of the conductive agent is 0.5-5%;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1), wherein the hot-pressing temperature is 60-250 ℃, the hot-pressing speed is 5-50 rpm, and the thickness is 30-500 um, so as to obtain the self-supporting anode material layer.
9. A positive electrode sheet, characterized in that it comprises the positive electrode material layer according to any one of claims 1 to 4;
preferably, the positive electrode sheet comprises a current collector and a positive electrode material layer according to any one of claims 1 to 4 on the surface of the current collector;
preferably, the current collector comprises an aluminum foil.
10. A semi-solid battery, characterized in that it comprises the positive electrode sheet of claim 9;
preferably, the semi-solid state battery includes any one of a lithium metal battery, a lithium ion battery, a lithium air battery, and a lithium sulfur battery.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114361379A (en) * 2021-12-08 2022-04-15 双登集团股份有限公司 Semi-solid battery with stable interface performance and manufacturing method thereof
WO2023039013A3 (en) * 2021-09-09 2023-04-13 The Chemours Company Fc, Llc Cathodes for high voltage lithium-ion secondary battery and dry method for manufacture of same
CN117012957A (en) * 2023-10-08 2023-11-07 深圳市贝特瑞新能源技术研究院有限公司 Low-temperature-resistant lithium iron phosphate semi-solid battery, positive electrode slurry thereof and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109004265A (en) * 2018-07-27 2018-12-14 江苏卓高新材料科技有限公司 Solid electrolyte anode and the solid state battery comprising it
CN110518250A (en) * 2019-09-06 2019-11-29 深圳先进技术研究院 Plasticizing anode of high positive active material carrying capacity and preparation method thereof, solid state battery
CN111276690A (en) * 2020-02-19 2020-06-12 中国科学院过程工程研究所 Low-porosity positive pole piece, preparation method thereof and application of positive pole piece in solid-state lithium metal battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109004265A (en) * 2018-07-27 2018-12-14 江苏卓高新材料科技有限公司 Solid electrolyte anode and the solid state battery comprising it
CN110518250A (en) * 2019-09-06 2019-11-29 深圳先进技术研究院 Plasticizing anode of high positive active material carrying capacity and preparation method thereof, solid state battery
CN111276690A (en) * 2020-02-19 2020-06-12 中国科学院过程工程研究所 Low-porosity positive pole piece, preparation method thereof and application of positive pole piece in solid-state lithium metal battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023039013A3 (en) * 2021-09-09 2023-04-13 The Chemours Company Fc, Llc Cathodes for high voltage lithium-ion secondary battery and dry method for manufacture of same
CN114361379A (en) * 2021-12-08 2022-04-15 双登集团股份有限公司 Semi-solid battery with stable interface performance and manufacturing method thereof
CN117012957A (en) * 2023-10-08 2023-11-07 深圳市贝特瑞新能源技术研究院有限公司 Low-temperature-resistant lithium iron phosphate semi-solid battery, positive electrode slurry thereof and preparation method thereof
CN117012957B (en) * 2023-10-08 2024-01-19 深圳市贝特瑞新能源技术研究院有限公司 Low-temperature-resistant lithium iron phosphate semi-solid battery, positive electrode slurry thereof and preparation method thereof

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