WO2024212909A1 - 改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法 - Google Patents

改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法 Download PDF

Info

Publication number
WO2024212909A1
WO2024212909A1 PCT/CN2024/086497 CN2024086497W WO2024212909A1 WO 2024212909 A1 WO2024212909 A1 WO 2024212909A1 CN 2024086497 W CN2024086497 W CN 2024086497W WO 2024212909 A1 WO2024212909 A1 WO 2024212909A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
diaphragm
powder
polyphenylene sulfide
manufacturing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2024/086497
Other languages
English (en)
French (fr)
Inventor
周海涛
高宏权
伍建春
周海云
姚圣杰
朱宏文
严荣飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202310393324.5A external-priority patent/CN117264212A/zh
Priority claimed from CN202410046169.4A external-priority patent/CN117878527A/zh
Application filed by Jiangsu University filed Critical Jiangsu University
Priority to US18/860,698 priority Critical patent/US12444807B2/en
Publication of WO2024212909A1 publication Critical patent/WO2024212909A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0431—Cells with wound or folded electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/136—Phenols containing halogens
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/049—Processes for forming or storing electrodes in the battery container
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H01M10/288—Processes for forming or storing electrodes in the battery container
    • 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
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H01M50/595—Tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • 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

Definitions

  • the present invention belongs to the technical field of secondary batteries, and specifically relates to a modified polyphenylene sulfide and a modification method thereof, a polyphenylene sulfide solid diaphragm, a prefabricated zinc salt diaphragm and a manufacturing method thereof, a zinc-manganese secondary battery and a manufacturing and application method thereof.
  • Aqueous zinc-manganese secondary batteries have the advantages of safety, environmental protection, abundant resources, and low cost, and have received widespread attention from researchers in recent years.
  • the commercial aqueous zinc-manganese secondary batteries of the ampere-hour level are difficult to apply and promote due to their short life and poor low-temperature performance.
  • the existing improvement method is to add low-temperature additives to the aqueous electrolyte, including alcohols, PEG, PVA, etc., to form a eutectic solution, effectively lowering the freezing point of the electrolyte, thereby developing low-temperature zinc-manganese secondary batteries.
  • the chance of side reactions will increase.
  • patent ZL202110122474.3 mentions the use of tetrachlorobenzoquinone as an anion adsorbent to form dipole adsorption with harmful components, increase the cation migration number of the diaphragm, and effectively inhibit the occurrence of side reactions.
  • tetrachlorobenzoquinone contains a high amount of chlorine, and long-term circulation will cause the current collector to corrode and fail.
  • Patent 202211223026.3 and Patent 202210355256.9 propose the use of a semi-dry process to manufacture the electrodes of zinc-manganese secondary batteries.
  • the use of dry electrode manufacturing process for zinc-manganese secondary batteries can effectively avoid a series of problems such as uneven slurry, difficult viscosity control, complex solvent removal, stratification of electrode components and powder loss of pole pieces during wet coating, but it also brings challenges.
  • the porosity of dry electrodes is low, less than 30%, resulting in low injection efficiency.
  • the concentration of zinc-manganese secondary battery electrolyte is high (>2mol/L), the viscosity is very large, and it is difficult to achieve uniform infiltration, resulting in very uneven distribution of electrolyte in the battery pole piece and diaphragm.
  • the wetting effect of the battery is generally improved by increasing the infiltration time and raising the shelf temperature, but this will undoubtedly waste a lot of time and electricity, greatly reducing the production efficiency of the battery.
  • the existing storage method usually injects electrolyte into the battery in advance, which makes the transportation and storage process As the storage time increases, the electrolyte in the battery will decompose, the battery capacity will decrease significantly, and it may even cause a short circuit in the battery, resulting in a waste of resources.
  • Chinese invention patent 202110380015.5 and patent application 202210444350.1 provide a sandwich structure composite diaphragm based on polyphenylene sulfide solid diaphragm. Although this diaphragm structure can effectively avoid dendrites, it still cannot solve the wetting problem of the aqueous diaphragm, resulting in uneven distribution of zinc salt inside the ampere-hour zinc-manganese secondary battery and poor battery consistency.
  • the present invention provides a modified polyphenylene sulfide suitable for long-life wide temperature range ampere-hour zinc-manganese secondary batteries and a method for manufacturing the same.
  • tetrachlorobenzoquinone in polyphenylene sulfide powder is subjected to chlorine reduction and hydrogenation reaction to generate chlorocatechol structure molecules, thereby improving the adsorption performance of polyphenylene sulfide-based solid diaphragms for harmful molecules.
  • the battery cycle stability is improved, the service temperature range of the battery is widened, and the low temperature resistance of the battery is improved.
  • a polyphenylene sulfide modification method suitable for a solid diaphragm of an ampere-hour zinc-manganese secondary battery with a long life and a wide temperature range is characterized in that polyphenylene sulfide powder, tetrachlorobenzoquinone and deionized water are mixed in a mass ratio of 10:0.25-0.75:1-12, and a hydrothermal reaction is carried out at 180-240°C. During the hydrothermal reaction, chloride ions are removed from tetrachlorobenzoquinone molecules and hydroxyl groups are increased, thereby generating molecules with a chlorocatechol structure.
  • the constant temperature time of the hydrothermal reaction temperature is 1-4 hours, and the reaction atmosphere is air, oxygen, nitrogen or argon.
  • the modified polyphenylene sulfide prepared by the polyphenylene sulfide modification method is characterized in that molecules with chlorocatechol structures are loaded in the polyphenylene sulfide solid diaphragm; the chlorocatechol molecules are one or a mixture of 2,5-dichlorohydroquinone, 2,3,5,6-tetrachlorophenol, 3,4,5-trichlorocatechol, tetrachlorohydroquinone, 3,4,6-trichlorocatechol and the like.
  • polyphenylene sulfide solid diaphragm made of the modified polyphenylene sulfide has zinc ion selective permeability.
  • the present invention also provides a prefabricated zinc salt diaphragm, a zinc-manganese secondary battery and a manufacturing method thereof.
  • the method During the manufacturing process of the prefabricated zinc salt diaphragm, the electrolyte zinc salt is prefabricated into the composite glue of the solid diaphragm and the upper and lower supporting diaphragms, which solves the problem that the high-concentration electrolyte in the zinc-manganese secondary battery is difficult to evenly infiltrate the inside of the battery pole piece, and can also produce a reserve zinc-manganese secondary battery that does not need to be filled with electrolyte during storage and transportation, thereby improving the production efficiency and battery performance of the zinc-manganese secondary battery.
  • the upper supporting membrane B and the lower supporting membrane F are both porous membranes, and the glue C and glue E are mixtures of organic adhesives and/or inorganic adhesives, electrolyte zinc salts, and solvents.
  • the mass ratio of the organic binder, the inorganic binder, the electrolyte salt and the solvent is 0-10: 0-10: 10-80: 10-80.
  • the organic adhesive is a mixture of one or more of polyvinyl alcohol (PVA), polyacrylate (PAA), and polytetrafluoroethylene (PTFE);
  • the inorganic adhesive is a mixture of one or more of sodium bentonite, zinc dihydrogen phosphate, and lithium montmorillonite powder;
  • the electrolyte zinc salt is a mixture of one or more of zinc trifluoromethanesulfonate, zinc sulfate, zinc chloride, and zinc perchlorate;
  • the solvent is a mixture of one or more of deionized water, nitrogen methyl pyrrolidone (NMP), alcohol, and propylene glycol.
  • NMP nitrogen methyl pyrrolidone
  • the thickness of the polyphenylene sulfide solid membrane A is 5-60 ⁇ m
  • the porous membrane is one of a polyethylene membrane (PE), a polypropylene membrane (PP), a cellulose membrane, a non-woven membrane, and a PET membrane, and the thickness thereof is 3-30 ⁇ m.
  • the dosage of the glue solution C and glue solution E is 5-30 mg/cm2; the drying temperature for both times is 50-100°C; after drying, the dry glue single layer load is 2-15 mg/cm2, and the thickness of the prefabricated zinc salt diaphragm H is 70-200 ⁇ m.
  • the prefabricated zinc salt diaphragm manufactured by the manufacturing method of the prefabricated zinc salt diaphragm is characterized in that it includes a polyphenylene sulfide solid diaphragm A and an upper supporting diaphragm B and a lower supporting diaphragm F located on both sides of the polyphenylene sulfide solid diaphragm A, and a mixture including an organic adhesive and/or an inorganic adhesive and an electrolyte salt is filled between the upper supporting diaphragm B, the lower supporting diaphragm F and the polyphenylene sulfide solid diaphragm A, and the mass ratio of the solid content is 0-10:0-10:10-80:10-80.
  • polyphenylene sulfide solid diaphragm A is made of the modified polyphenylene sulfide.
  • the manufacturing equipment of the polyphenylene sulfide solid diaphragm A includes a powder processing system, a high-speed shearing machine, a screw extruder, a horizontal cold roller press, and a horizontal hot roller press;
  • the powder processing system includes an air compressor, an air storage tank, a cold dryer, a drying adsorption tower, a purification column, an air preheating system, a powder heating system, a supersonic shear mixer, and a gas-solid separation tower which are connected in sequence;
  • the supersonic shear mixer has a semi-closed cavity, the air outlet of the purification column is connected to the air inlet of the semi-closed cavity of the supersonic shear mixer, and the air preheating system is arranged on the air pipeline between the purification column and the supersonic shear mixer;
  • the powder heating system is arranged at the discharge port of the semi-closed cavity of the supersonic shear mixer;
  • the discharge port of the semi-closed cavity of the supersonic shear mixer is connected to the gas-solid separation tower through a pipeline, and the gas-solid separation tower is provided with an air outlet at the top, a discharge port at the bottom, and an air hammer air inlet in the middle;
  • the powder processed by the powder processing system is sent to the high-speed shearing machine, and enters the screw extruder after shearing.
  • the horizontal cold roller press and the horizontal hot roller press are arranged downstream of the screw extruder in sequence, and a heating conveying guide rail is arranged between the horizontal cold roller press and the horizontal hot roller press.
  • drying adsorption towers which are arranged in parallel and respectively connected to the air outlet of the cold dryer and the air inlet of the purification column; the gas source of the air hammer is the dry compressed air bypass after the purification column, and the air hammer function is realized by intermittently releasing compressed air.
  • the method for manufacturing the polyphenylene sulfide solid diaphragm A comprises the following steps:
  • the metal chloride A is dissolved in deionized water to prepare a solution B, tetrachlorobenzoquinone and polyphenylene sulfide powder are mixed to prepare a mixed powder C, the solution B and the mixed powder C are mixed to prepare a slurry D, the slurry D is loaded into a closed reactor for hydrothermal reaction, and after the reaction is completed, the powder is washed and neutrally dried to prepare a powder E;
  • the polytetrafluoroethylene powder and powder E are uniformly mixed in a mixer to obtain powder F, and the mixing process is carried out under the temperature condition that the polytetrafluoroethylene is in a glassy state;
  • the dry air G After being compressed, cold-dried, dry-adsorbed, purified, and preheated by an air compressor, the dry air G passes through a nozzle and enters a semi-enclosed cavity, where it is accelerated to supersonic speed, forming a supersonic jet H of extremely dry air;
  • the powder F is preheated and added into the semi-enclosed cavity, where it is frictionally sheared by the supersonic jet H of extremely dry air.
  • the molecular chains of polytetrafluoroethylene in the powder F are extended and opened, forming physical adhesion with the powder in F without chemical reaction, thereby obtaining powder I.
  • the powder I is blown into the solid-gas separation tower along with the air flow.
  • the gas is discharged directly, and the powder adhering to the filter element is blown into the receiving barrel below by the air hammer;
  • the powder I is added to a high-speed shearing machine for secondary fiberization, and then enters a screw extruder to be extruded into a plurality of continuous thick strips or continuous thick cakes J, and enters a horizontal cold roller press for primary thinning. After thinning, it enters a heated conveying guide rail, and enters a horizontal hot roller press while being heated and fed for secondary thinning. The two edges are cut off to form a finished solid diaphragm L, which is then rolled up.
  • the metal chloride A in the powder making process is one or a mixture of lithium chloride, sodium chloride, zinc chloride, magnesium chloride, and aluminum chloride;
  • the polyphenylene sulfide powder is a cross-linked high-crystalline polyphenylene sulfide powder with a crystallinity of >60% and a D50 of 3-25 ⁇ m;
  • the mass ratio of the metal chloride, deionized water, tetrachlorobenzoquinone, and polyphenylene sulfide is 0-3:3-30:0.1-0.75:5-15;
  • the atmosphere in the hydrothermal reactor is air or argon, the hydrothermal reaction temperature is 150-250°C, and the hydrothermal reaction time is 1-4 hours; and the volume filling rate of the hydrothermal reaction is 20%-70%.
  • the relative humidity (RH) of the dry air G at room temperature of 25°C is ⁇ 10%; the power of the air compressor is greater than or equal to 15kW, and preferably greater than 30kW for continuous production; the dew point of the supersonic jet H of the extremely dry air is lower than -40°C; the dry adsorption process is to use multiple dry adsorption towers containing molecular sieves, the total weight of the molecular sieves is >200kg, and the multiple dry adsorption towers work and regenerate alternately, and the alternation time is 3-12 minutes.
  • the preheating temperature of the air before entering the nozzle is 30-60°C
  • the preheating temperature of the powder F entering the semi-enclosed cavity is 40-220°C.
  • the plurality of continuous thick strips or continuous thick cakes J whose shapes are determined by the extrusion head die of the screw extruder, the diameter of the continuous thick strips or the thickness of the continuous thick cakes are between 3-12 mm; the roller surface temperature of the horizontal cold roller press is -10-30°C; the thickness after the first thinning is 0.3-1.5 mm; the temperature of the heated conveying rail is 90-150°C; the roller surface temperature of the horizontal hot roller press is 110-160°C; the thickness after the secondary thinning is 5-60 ⁇ m.
  • the method for manufacturing a zinc-manganese secondary battery made of the prefabricated zinc salt diaphragm is characterized in that the prefabricated zinc salt diaphragm H is placed between the manganese oxide positive electrode and the zinc negative electrode, and the tabs are welded, and a battery cell is prepared by using a stacking machine or a winding machine, and is placed in a battery shell or an aluminum-plastic film bag, packaged for standby use, and stored; a sealable liquid injection port is left on the battery shell or the aluminum-plastic film bag.
  • the manganese oxide positive electrode is a manganese dioxide dry electrode manufactured by semi-dry process technology, and the manganese oxide is one of ⁇ -MnO 2 , ⁇ -MnO 2 , ⁇ -MnO 2 , ⁇ -MnO 2 , Mn 2 O 3 , Mn 3 O 4 , LiMn 2 O 4 or a mixture of several thereof;
  • the zinc negative electrode is one of zinc powder dry electrode, zinc foil, and galvanized copper foil manufactured by semi-dry process technology.
  • the welding point is provided with water-blocking insulation protection.
  • the water-blocking insulation protection of the welding point is achieved by wrapping with a water-blocking insulation tape, coating with an aluminum oxide layer or applying resin protection;
  • the resin is one or more of epoxy resin, phenolic resin, furan resin, and unsaturated polyester;
  • the pole ear is a nickel pole ear, a copper pole ear, a titanium pole ear or a molybdenum pole ear.
  • an external supporting mechanism is required to increase the preload force between the prefabricated zinc salt separator H, the manganese oxide positive electrode and the zinc negative electrode, and reduce the inter-electrode distance so that the inter-electrode distance is controlled at 50-120 ⁇ m.
  • the outer packaging of the battery shell adopts a water-blocking, gas-blocking, and acid-resistant material, and the water-blocking, gas-blocking, and acid-resistant material is a non-porous film.
  • non-porous film is preferably a composite film of one or more of biaxially oriented polypropylene film (BOPP), cast polypropylene film (CPP), polyethylene terephthalate (PET), polyethylene (PE), and polypropylene (PP) non-porous films.
  • BOPP biaxially oriented polypropylene film
  • CPP cast polypropylene film
  • PET polyethylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • the manufacturing method of the manganese oxide positive electrode comprises the following steps: firstly, manganese dioxide is mixed with polytetrafluoroethylene, and below the glass transition temperature of polytetrafluoroethylene, dry supersonic jet gas is used to open the molecular chain of polytetrafluoroethylene and physically adhere to the positive electrode material powder, and then an alcohol solution is sprayed on the fiberized powder, and after banburying and shearing granulation, hot rolling is performed to form a positive electrode film, and then the multi-layer positive electrode film is compounded into a composite positive electrode self-supporting film with a thickness of 100-150 ⁇ m through multiple cold rolling, and finally the composite positive electrode self-supporting film is compounded with a sandblasted stainless steel foil with a glue-coated surface through a hot rolling machine.
  • the method for manufacturing the zinc negative electrode comprises the following steps:
  • the polytetrafluoroethylene powder and powder A are mixed in a mixer to form powder B; the mixing process is carried out at a temperature where the polytetrafluoroethylene (PTFE) is in a glassy state;
  • PTFE polytetrafluoroethylene
  • the powder B and the alcohol-water mixed solvent are in a ball mill, and the ball mill beads are constantly rubbed during high-speed rotation to make the PTFE wire drawing present a mesh structure, the molecular chain of the polytetrafluoroethylene in the powder B is extended and opened, and forms physical adhesion with the powder in the powder A, and the hydrogen evolution inhibitor reacts with the surface of the zinc powder by reduction reaction.
  • the micelle C is obtained by filtration;
  • the micelle C is kneaded to form a uniform micelle, which is then sheared and granulated to form millimeter-sized granules E of uniform size;
  • the granular material E is hot-pressed into a negative electrode film F by a horizontal hot roller press, and a porous release paper is used as a support belt to complete the winding.
  • the negative electrode film F covered with the release paper is dried as a whole roll to remove part of the solvent;
  • the semi-dried negative electrode film F after the release paper is peeled off is thermally laminated on both sides of the glue-coated stainless steel foil to form an electrode by using a hot pressing composite process;
  • the zinc powder is powdered particles with a particle size of 5-20 ⁇ m;
  • the conductive agent is one or two of super-P and ECP, and the toughening conductive agent is one or a mixture of artificial graphite and high-purity graphite;
  • the cationic slow-release agent is an inorganic powder with electronegativity and volume expansion when in contact with water;
  • the hydrogen evolution inhibitor is a metal compound that can undergo a reduction reaction with the zinc powder in an alcohol-water solvent;
  • the weight percentages of zinc powder, conductive agent, toughening conductive agent, cationic slow-release agent, polytetrafluoroethylene, and hydrogen evolution inhibitor powder are: 60%-90%: 1%-10%: 1%-10%: 1%-10%: 3%-15%: 0.1%-5%.
  • the cationic sustained-release agent is one or more of bentonite, montmorillonite powder, illite powder, kaolin powder, and halloysite powder; and the hydrogen evolution inhibitor is one or more of indium chloride, copper chloride, indium sulfate, and copper sulfate.
  • the alcohol-water mixed solvent is a mixed solvent of water and isopropanol, propylene glycol or ethanol, and the volume percentage of water to alcohol is: 40%-80%: 20%-60%; the solid content of the uniform micelle is 40%-60%.
  • the granular material E is rolled once by a horizontal hot roller press to achieve a negative electrode film F with a thickness of 90-200 ⁇ m, and the hot roller pressing temperature is 55-95° C.
  • the adhesive-coated stainless steel foil is sandwiched between two negative electrode films F with the release paper removed, unwound at the same speed, and enters two relatively rotating horizontal hot roller presses.
  • the rolling temperature is 30-120°C.
  • the glue-coated stainless steel foil is obtained by printing a highly conductive paste on both sides of the stainless steel foil using a gravure printing machine.
  • the surface of the stainless steel foil needs to be sandblasted before glue coating to remove surface rolling oil.
  • the highly conductive paste is composed of high-purity graphite, a non-hydrophilic adhesive and a non-aqueous solvent.
  • the remarkably zinc-manganese secondary battery manufactured by the remarkably zinc-manganese secondary battery manufacturing method is characterized in that it consists of a manganese oxide positive electrode, a zinc negative electrode, a three-layer prefabricated zinc salt diaphragm H and a battery shell or an aluminum-plastic film bag with a sealable liquid injection port, and the manganese oxide positive electrode, the zinc negative electrode and the three-layer prefabricated zinc salt diaphragm H are placed in the battery shell or the aluminum-plastic film bag after the tabs are welded.
  • the application method of the rechargeable zinc-manganese secondary battery is characterized in that the rechargeable zinc-manganese secondary battery does not need to be injected during storage and transportation; before being put into use, pure water, seawater or dilute electrolyte is injected into the battery; preferably, the dilute electrolyte is a salt solution of one or more of zinc sulfate, sodium sulfate, magnesium sulfate, sodium chloride, and zinc trifluoromethanesulfonate with a concentration of 0.01 mol/L to 1 mol/L, and its solvent is a mixture of one or more of water, ethanol, methanol, propylene glycol, isopropanol, and glycerol; preferably, the amount of injected liquid is 1-20 mL/Ah.
  • the formation method of the remarked zinc-manganese secondary battery is characterized in that, during the battery formation process, an electrolyte with only water as a solvent is first injected into the secondary battery, and a discharge is performed once with a small current formation with a current density of 1-20 mA/g, and then 0-40 cycles of charge and discharge are performed. After that, an organic solvent is injected in the battery discharge state, and then vacuum packaging is performed.
  • the organic solvent is an organic solvent that can lower the freezing point of water after mixing with water, and the volume ratio of the aqueous solution electrolyte to the organic solvent is 5:0.3-5.
  • the electrolyte with water as solvent is a 2-3 mol/L aqueous solution of zinc trifluoromethanesulfonate, a 2-3 mol/L aqueous solution of zinc sulfate or a 2-3 mol/L aqueous solution of zinc chloride; and the injection volume is 3-10 mL/Ah.
  • the organic solvent is alcohol, dimethyl sulfoxide, propylene carbonate, or acetonitrile.
  • the alcohol is one or a mixture of methanol, isopropanol, ethylene glycol, propylene glycol, and glycerol.
  • the manufacturing method of the prefabricated zinc salt diaphragm of the present invention is to prefabricate the electrolyte zinc salt into the composite glue liquid of the solid diaphragm and the upper and lower supporting diaphragms during the diaphragm manufacturing process to prepare the composite diaphragm of the prefabricated zinc salt.
  • the zinc-manganese secondary battery made of the prefabricated zinc salt diaphragm has the advantage that no electrolyte needs to be injected during storage and transportation.
  • the zinc-manganese secondary battery When the zinc-manganese secondary battery is put into use, it only needs to inject pure water, seawater or low-viscosity dilute electrolyte into the battery, which not only effectively solves the problem that high-concentration electrolyte is difficult to evenly infiltrate the inside of the battery pole piece during the manufacturing process of the zinc-manganese secondary battery, thereby improving the battery performance, but also simplifies the manufacturing steps and production efficiency of the secondary battery, and improves the storage and transportation performance.
  • the zinc-manganese secondary battery when the zinc-manganese secondary battery is in use, it is only necessary to add a liquid that can form an aqueous electrolyte environment to the battery housing or aluminum-plastic film bag to ensure the normal charging and discharging of the zinc-manganese secondary battery.
  • the added solution has a wide range of selectivity, including water, zinc-containing solutions, and solutions of different cations, such as seawater, etc., to form a double cation or multi-cation system, and the positive electrode reaction is diversified.
  • the zinc ions in the prefabricated zinc salt diaphragm are dissolved, and at this time, the electrolyte only contains zinc ions, and the surface of the manganese oxide positive electrode is a dissolution ⁇ deposition reaction of zinc-containing manganese oxide; if seawater is added, the zinc ions in the prefabricated zinc salt diaphragm are dissolved and the sodium ions and magnesium ions added to the seawater form a multi-ion system, and the smaller sodium ions will be embedded in the manganese oxide.
  • the coexistence of ion embedding ⁇ extraction mechanism and dissolution ⁇ deposition mechanism in the positive electrode can greatly increase the capacity of the aqueous secondary battery.
  • the multi-cation system can also improve the zinc deposition kinetics, effectively avoid dendrites, and improve the cycle stability of the system.
  • the prefabricated zinc salt diaphragm and the pre-assembled zinc-manganese secondary battery of the present invention have the following advantages:
  • the manufacturing method of the modified polyphenylene sulfide suitable for long-life wide-temperature range ampere-hour zinc-manganese secondary battery of the present invention adopts a simple hydrothermal synthesis method, and uses cheap deionized water as a reactant to provide protons.
  • tetrachlorobenzoquinone removes part of the chloride ions, and the quinone group is hydrogenated to become a hydroxyl group, forming an electron-withdrawing group that is more easily combined with anions.
  • the generated chlorocatechol structure is more easily dipole adsorbed with anions, fluorides, chlorides, hydrides, etc., thereby cutting off the shuttling of harmful molecules between the positive and negative electrodes of the zinc-manganese secondary battery, and greatly improving the ion migration number of the polyphenylene sulfide solid diaphragm.
  • the generated chlorocatechol has a lower melting point, which can help the polyphenylene sulfide diaphragm soften at a processing temperature of 100 to 200°C to form a thinner, A non-porous solid diaphragm with a smoother surface.
  • the air source used in the fiberization process is dry atmospheric air, and the relative humidity (RH) is ⁇ 10% at room temperature of 25°C.
  • the purpose is to achieve extremely dry air with a dew point of -40°C after the cold drying and dry adsorption steps of the production line, so as to minimize the energy consumed in the air drying process.
  • the purpose of obtaining extremely dry air is to enable PTFE to be better fiberized, and to prevent moisture absorption caused by high static electricity of PTFE fibers after shear friction, so that subsequent film pressing produces broken belts.
  • a horizontal cold roller press is first used to thin the continuous thick strips or continuous thick cakes once.
  • the temperature at this time needs to be below the softening temperature of PPS (130°C), and the purpose is only to control the uniform feeding of subsequent hot roller pressing.
  • the purpose of using a heated conveying guide rail is to heat the continuous thin cake (0.3-1.5mm) after the first thinning to above the deformation temperature of PPS. After passing through the horizontal hot roller press, the PPS crystal particles undergo thermoplastic deformation and can be better pressed into a film. After the two sides of the hot-pressed film are trimmed, the trimmed material can be recycled to the high-speed shearing machine, so that the utilization rate of the powder reaches 100%, further reducing the cost.
  • the prepared polyphenylene sulfide solid diaphragm has the following characteristics: low porosity; high conductivity; high ion migration number; strong ion selectivity; obvious ion rectification effect, and effective inhibition of metal negative electrode dendrites.
  • the positive and negative electrodes of the present invention are prepared by a semi-dry method, and the powders of the positive and negative electrodes are entangled and bundled by fibrous PTFE. During the charge and discharge process, the dissolution/deposition of the positive and negative electrode materials will not cause the electrode to be pulverized.
  • the surface of the zinc powder is treated by chemical indium plating, chemical copper plating, acetic acidification or phosphorylation, which effectively inhibits the hydrogen evolution of the zinc powder.
  • Cationic chelating agents and the like are added to the semi-dry zinc negative electrode to stabilize the change in ion concentration in the electrolyte, thereby obtaining a more stable cycle.
  • inorganic powders such as bentonite, montmorillonite powder, illite powder, kaolin powder, and halloysite powder are introduced into the semi-dry zinc negative electrode, and the volume expands several to dozens of times after contacting water, and the water is effectively fixed, the solid content of the micelle is reduced, and the micelle is prevented from sticking to the roller in the subsequent film pressing process due to excessive amount of solvent.
  • the volume of the inorganic powder shrinks, and the pores are introduced, thereby improving the porosity of the semi-dry electrode.
  • Inorganic powders such as bentonite, montmorillonite powder, illite powder, kaolin powder, and halloysite powder have strong electronegativity and can effectively absorb excess cations (Mn 2+ , H + , Zn 2+ ) in the electrolyte through the layered crystal structure, thereby playing a role in sustained release of cations, slowing down the large fluctuations in cations (Mn 2+ , H + , Zn 2+ ) in the electrolyte caused by the dissolution/deposition of active substances, stabilizing the pH value of the electrolyte, and providing high reversibility of the system.
  • the present invention directly introduces a hydrogen evolution inhibitor during the ball milling fiberization process.
  • the zinc negative electrode has the following characteristics: (1) it can effectively inhibit dendrites; (2) it has a cation sustained release effect; (3) it has an excellent three-dimensional conductive network and many stripping/deposition active sites; (4) the PTFE entanglement network structure is stable; (5) the porosity is large; (6) it can effectively avoid hydrogen evolution at the zinc negative electrode.
  • the present invention performs water-blocking and insulating protection measures on the welding points, which is very important during the cycle of the zinc-manganese secondary battery. If the welding points are in contact with the electrolyte, electrochemical corrosion is very likely to occur during the charge and discharge process, resulting in low battery energy efficiency and even short circuit failure.
  • An external support mechanism is added to reduce the inter-electrode distance and strengthen the close fit between the pole pieces, thereby avoiding the side reactions of hydrogen and oxygen evolution caused by excessive inter-electrode distance. The occurrence of side reactions of the battery during the charge and discharge process is greatly avoided, thereby ensuring the cycle stability of the battery and greatly improving the electrochemical performance of the battery; without affecting the battery capacity, rate performance and energy density, the service temperature of the battery is broadened.
  • the present invention adopts glue-coated sandblasted stainless steel. After sandblasting, the rolling oil is removed from the surface of the stainless steel, and the rough surface has stronger adhesion with the conductive layer and the zinc powder negative electrode film.
  • the coated conductive glue layer is a mixture of high-purity graphite and a non-hydrophilic adhesive, which can effectively prevent water from corroding the stainless steel collector and prevent the electrode film and the collector foil from falling off.
  • an electrolyte with only water as a solvent is first injected for preliminary formation, and then an alcohol solvent is added for formation. This avoids excessive participation of alcohol in side reactions during the initial cycle, resulting in the generation of more harmful impurities.
  • a hydrated solid electrolyte layer is preferentially constructed to form a stable zinc ion migration shell.
  • alcohol is introduced to reduce the freezing point of the solvent, avoid precipitation of electrolyte salt at low temperatures, and stabilize and widen the working temperature of the electrolyte.
  • FIG1 , FIG2 , and FIG3 are pyrolysis gas chromatography-mass spectrometry (PGC-MS) of polyphenylene sulfide powder modified by hydrothermal reaction, which are used to confirm the presence of chlorocatechol-like structural molecules in the reaction product.
  • PLC-MS pyrolysis gas chromatography-mass spectrometry
  • FIG. 4 is a comparison photo of the H-type cell before and after electrodialysis in the selective permeability test of the polyphenylene sulfide solid membrane in Example 2.
  • FIG. 4 is a comparison photo of the H-type cell before and after electrodialysis in the selective permeability test of the polyphenylene sulfide solid membrane in Example 2.
  • FIG5 is a schematic diagram of the structure of the prefabricated zinc salt diaphragm of the present invention.
  • FIG6 is a picture of the prefabricated zinc salt membrane in Example 1.
  • FIG. 7 is a schematic diagram of the battery core structure of the remarked zinc-manganese secondary cylindrical battery after winding is completed in the present invention.
  • FIG8 is a graph showing the charge and discharge of the remarked zinc-manganese secondary cylindrical battery in Example 1 after being filled with seawater.
  • FIG. 9 is a charge and discharge cycle diagram of the remarked zinc-manganese secondary cylindrical battery in Example 1 after being filled with seawater.
  • FIG. 10 is a comparison of the capacities of the zinc-manganese secondary cylindrical batteries of Example 3-7 after being filled with different electrolytes.
  • FIG. 11 is a laminated core pack of a zinc-manganese secondary battery in Example 8 before welding point protection.
  • FIG. 12 is a laminated core package of a zinc-manganese secondary battery after welding point protection in Example 8.
  • FIG. 12 is a laminated core package of a zinc-manganese secondary battery after welding point protection in Example 8.
  • FIG. 13 is a diagram of a zinc-manganese secondary battery packaged in aluminum-plastic film in Example 8.
  • FIG. 14 is a stable cycle curve of the remarked zinc-manganese secondary battery in Example 8 after undergoing a water-first-then-alcohol formation system.
  • FIG. 15 is a charge and discharge curve at 7° C. of the remarked zinc-manganese secondary battery in Example 9 after the formation system of first water and then alcohol.
  • FIG. 16 is a charge and discharge curve at 0° C. of the remarked zinc-manganese secondary battery in Example 10 after the formation system of first water and then alcohol.
  • FIG. 17 is a charge and discharge curve at -10° C. of the remarked zinc-manganese secondary battery in Example 11 after the formation system of first water and then alcohol.
  • FIG. 18 is a schematic diagram of the structure of the powder processing system described in Example 12.
  • FIG. 19 is a flow chart of the film formation of the polyphenylene sulfide solid diaphragm A described in Example 12.
  • FIG. 20 is a surface SEM image of the polyphenylene sulfide solid diaphragm A described in Example 13.
  • FIG. 21 is a cross-sectional SEM image of the polyphenylene sulfide solid diaphragm A described in Example 13.
  • FIG22 is a surface SEM image of the negative electrode film described in Example 18.
  • Example 23 is a SEM image of the spatial entangled network structure composed of PTFE in the cross section of the negative electrode membrane described in Example 18.
  • the polyphenylene sulfide modification method suitable for the solid diaphragm of long-life wide-temperature range ampere-hour zinc-manganese secondary battery is as follows: after the three raw materials of polyphenylene sulfide powder, tetrachlorobenzoquinone and deionized water are mixed, a hydrothermal reaction is carried out, the hydrothermal reaction temperature is 180-240°C, the constant temperature time is 1-4 hours, and the reaction atmosphere is air, oxygen, nitrogen or argon.
  • the mass ratio of the three raw materials of polyphenylene sulfide powder, tetrachlorobenzoquinone and deionized water is 10:0.25-0.75:1-12.
  • the tetrachlorobenzoquinone molecule undergoes a reaction of removing chloride ions and increasing hydroxyls, generating molecules of chlorocatechol structure, including 2,5-dichlorohydroquinone, 2,3,5,6-tetrachlorophenol, 3,4,5-trichlorocatechol, tetrachlorohydroquinone, 3,4,6-trichlorocatechol, etc., or a mixture of several thereof.
  • the three raw materials of polyphenylene sulfide powder, tetrachlorobenzoquinone and deionized water were mixed in a mass ratio of 10:0.5:3, and a hydrothermal reaction was carried out at 210°C for 2 hours in an air atmosphere.
  • the obtained powder was detected by pyrolysis gas chromatography-mass spectrometry (PGC-MS), and it was found that the tetrachlorobenzoquinone molecules underwent a reaction of removing chloride ions and increasing hydroxyls, generating molecules with chlorocatechol structures, including 2,5-dichlorohydroquinone, 3,4,5-trichlorocatechol, and tetrachlorohydroquinone, as shown in Figures 1, 2, and 3, respectively.
  • PPC-MS pyrolysis gas chromatography-mass spectrometry
  • the three raw materials of polyphenylene sulfide powder, tetrachlorobenzoquinone and deionized water were mixed in a mass ratio of 10:0.5:6, and hydrothermally reacted at 210°C for 2 hours in an air atmosphere.
  • the obtained powder was detected by pyrolysis gas chromatography-mass spectrometry (PGC-MS), and it was found that the tetrachlorobenzoquinone molecules underwent a reaction of removing chloride ions and increasing hydroxyl groups, generating molecules with chlorocatechol structures, including 2,5-dichlorohydroquinone, 3,4,5-trichlorocatechol, tetrachlorohydroquinone and 3,4,6-trichlorocatechol.
  • PPC-MS pyrolysis gas chromatography-mass spectrometry
  • the composition of the mother liquor was 1 mol/L ZnSO 4 , 0.1 mol/L Na 2 SO 4 , 0.1 mol/L Li 2 SO 4 , 0.1 mol/L MnSO 4 , 0.1 mol/L NiSO 4 , 0.1 mol/L CoSO 4 , 0.1 mol/L CuSO 4 , 0.1 mol/L FeSO 4 , 0.1 mol/L K 2 SO 4 , and 0.1 mol/L MgSO 4 .
  • Both the anode and cathode used Pt metal electrodes, and the electrodialysis test was carried out for 24 hours with a cell voltage of 3.25V.
  • Figure 4 shows the comparison of the H-type cell before and after electrodialysis.
  • the dilute sulfuric acid in the left cathode cell did not change color, there was a lot of sediment under the electrode, and there was a lot of sediment and a small amount of bubbles on the surface of the Pt electrode.
  • the anode cell on the right still had heavy metals. Dark brown.
  • Table 1 shows the changes in the concentration of metal ions in the mother solution before and after electrodialysis measured by ICP. It is confirmed that only zinc ions pass through the polyphenylene sulfide solid separator A, which is the core factor to ensure that the zinc-manganese secondary battery has good performance.
  • Table 1 shows the changes in the concentration of metal ions in the mother liquor before and after electrodialysis
  • the prefabricated zinc salt diaphragm of the present invention comprises a polyphenylene sulfide solid diaphragm A and an upper supporting diaphragm B and a lower supporting diaphragm F located on both sides of the polyphenylene sulfide solid diaphragm A, and a mixture of an organic adhesive and/or an inorganic adhesive and an electrolyte zinc salt is filled between the upper supporting diaphragm B, the lower supporting diaphragm F and the polyphenylene sulfide solid diaphragm A, respectively.
  • the content of the glue C between the upper supporting membrane B and the polyphenylene sulfide solid membrane A and the glue E between the upper supporting membrane B, the lower supporting membrane F and the polyphenylene sulfide solid membrane A can be the same or different.
  • the ratio of the organic binder, the inorganic binder, the electrolyte salt and the solvent in the glue C and the glue E is 0-10: 0-10: 10-80: 10-80, and the amount of the glue C and the glue E is 5-30 mg/ cm2 ; after drying, a solid mixed glue layer is formed, and the dry glue single layer load is 2-15 mg/ cm2 , and the thickness of the prefabricated zinc salt membrane is 70-200 ⁇ m.
  • the organic binder is a mixture of one or more polymer binders such as polyvinyl alcohol (PVA), polyacrylate (PAA), polytetrafluoroethylene (PTFE), etc.;
  • the inorganic binder is a mixture of one or more inorganic powders such as sodium bentonite, zinc dihydrogen phosphate, lithium montmorillonite powder, etc.;
  • the electrolyte salt is a mixture of one or more inorganic salts such as zinc trifluoromethanesulfonate, zinc sulfate, zinc chloride, zinc perchlorate, etc.;
  • the solvent is deionized water, nitrogen methyl pyrrolidone (NMP), alcohol A mixture of one or more solvents such as alcohol, propylene glycol, etc.
  • the thickness of the polyphenylene sulfide solid diaphragm A is 5-60 ⁇ m.
  • the upper support diaphragm B and the lower support diaphragm F are both porous diaphragms, and their materials and thicknesses can be the same or different; they are selected from porous diaphragms such as polyethylene diaphragms (PE), polypropylene diaphragms (PP), cellulose membranes, non-woven fabric membranes, PET membranes, etc. with a thickness of 3-30 ⁇ m.
  • the method for preparing the prefabricated zinc salt diaphragm can be done by dipping the glue from the glue storage tank, or by coating the diaphragm to form the glue, and then compounding the three layers of diaphragm.
  • the following embodiment takes the dipping method as an example for specific description.
  • the remarked zinc-manganese secondary battery comprises a positive electrode, a negative electrode and the prefabricated zinc salt diaphragm.
  • the prefabricated zinc salt diaphragm H is placed between the manganese oxide positive electrode and the zinc negative electrode, and the tabs are welded.
  • the battery cell is prepared by using a laminating machine or a winding machine, and is placed in a battery shell with a sealable liquid injection port or an aluminum-plastic film bag, and packaged for standby and storage.
  • the manganese oxide positive electrode is a manganese dioxide dry electrode manufactured by semi-dry process technology
  • the manganese oxide is a mixture of one or more manganese oxides such as ⁇ -MnO 2 , ⁇ -MnO 2 , ⁇ -MnO 2 , ⁇ -MnO 2 , Mn 2 O 3 , Mn 3 O 4 , LiMn 2 O 4 , etc.
  • the zinc negative electrode is one of zinc powder dry electrode, zinc foil, galvanized copper foil, etc. manufactured by semi-dry process technology.
  • the remarked zinc-manganese secondary battery does not need to be injected during storage; when the battery needs to be used, pure water, seawater or dilute electrolyte is injected into the battery, and the amount of liquid injected is 1-20mL/Ah. After the injection port is sealed, a zinc-manganese secondary battery capable of charge and discharge is obtained.
  • the dilute electrolyte is a salt solution of zinc sulfate, sodium sulfate, magnesium sulfate, sodium chloride, zinc trifluoromethanesulfonate, etc.
  • the dilute electrolyte can also be directly seawater.
  • Example 3 Prefabricated zinc salt diaphragm and zinc-manganese secondary battery
  • the polyphenylene sulfide solid diaphragm A enters the laminating machine through the guide rail, and the upper supporting diaphragm B is dipped into the glue C through the glue tank where the glue C is stored, and the excess glue is scraped off by a scraper, and is compounded with the polyphenylene sulfide solid diaphragm A on the platform, and then the upper supporting diaphragm B and the solid diaphragm A are compounded by rolling.
  • the upper supporting diaphragm B is a hydrophilic polyethylene diaphragm (PE), and the glue C is composed of polyvinyl alcohol (PVA), zinc dihydrogen phosphate, electrolyte salt zinc trifluoromethanesulfonate and water, and the mass ratio of the four is 1:1:50:48.
  • the composite diaphragm is dried in a tunnel furnace and then cut to obtain a double-layer prefabricated zinc salt diaphragm D, which is then rolled up.
  • the temperature of the tunnel furnace is 70°C.
  • the polyphenylene sulfide side of the double-layer prefabricated zinc salt diaphragm D is passed through the glue tank for storing the glue E to pick up the glue E, and the excess glue is scraped off by a scraper, and compounded with the lower support membrane F at the platform, and then the lower support membrane F and the double-layer prefabricated zinc salt diaphragm D are completed by rolling.
  • the support membrane F is a hydrophilic polyethylene film (PE)
  • the glue E is composed of polyvinyl alcohol (PVA), sodium bentonite, electrolyte salt zinc trifluoromethanesulfonate and water, and the mass ratio of the four is 1:1:50:48.
  • the three-layer diaphragm after compounding is dried in a tunnel furnace to obtain a three-layer prefabricated zinc salt diaphragm H, and then rolled up.
  • the temperature of the tunnel furnace is 70°C.
  • the appearance of the prefabricated zinc salt diaphragm made in this embodiment is shown in Figure 6.
  • the ⁇ - MnO2 dry electrode and the dry electrode made of zinc powder are used as the positive and negative electrodes respectively, and are wound with the prefabricated zinc salt separator H to form a battery core, which is loaded into a 18650 battery shell to make a remark zinc-manganese secondary cylindrical battery.
  • Figure 7 is a schematic diagram of the structure of the battery core after the remark zinc-manganese secondary cylindrical battery is wound.
  • Figure 8 is a curve diagram of the charge and discharge of the remark zinc-manganese secondary cylindrical battery in this embodiment after the seawater is filled, and its charge and discharge curve is consistent with the curve of the conventional zinc-manganese secondary battery.
  • Figure 9 is a cycle diagram of the charge and discharge of the remark zinc-manganese secondary cylindrical battery in this embodiment after the seawater is filled. The battery cycle is stable, and there is no obvious attenuation after 150 cycles.
  • the present embodiment affixes insulating water-proof tape to the exposed part of the current collector of the ⁇ - MnO2 dry electrode and the dry electrode made of zinc powder for protection, and the stainless steel current collector and the pole ear are welded together by resistance welding.
  • the outer packaging of the remark zinc-manganese secondary battery is made of PP material, and there is a supporting mechanism on the outside, which reduces the inter-pole distance to 65 ⁇ m.
  • Example 4 Prefabricated zinc salt diaphragm and zinc-manganese secondary battery
  • the polyphenylene sulfide solid diaphragm A enters the laminating machine through the guide rail, and the upper supporting diaphragm B is dipped into the glue C through the glue tank where the glue C is stored, and the excess glue is scraped off by a scraper, and is compounded with the polyphenylene sulfide solid diaphragm A on the platform, and then the upper supporting diaphragm B and the solid diaphragm A are compounded by rolling.
  • the upper supporting diaphragm B is a hydrophilic polypropylene diaphragm (PP), and the glue C is composed of polyacrylate (PAA), zinc dihydrogen phosphate, electrolyte salt zinc trifluoromethanesulfonate and water, and the mass ratio of the four is 1:2:45:52.
  • PAA polyacrylate
  • the composite diaphragm is dried in a tunnel furnace and then cut to obtain a double-layer prefabricated zinc salt diaphragm D, and rolled up.
  • the temperature of the tunnel furnace is 80°C.
  • the polyphenylene sulfide side of the double-layer prefabricated zinc salt diaphragm D is passed through the glue tank for storing the glue E to pick up the glue E, and the excess glue is scraped off by a scraper, and then compounded with the lower support film F on the platform, and then rolled to complete.
  • the lower support membrane F is composited with the double-layer prefabricated zinc salt membrane D.
  • the support membrane F is a hydrophilic polyethylene film (PE)
  • the glue E is composed of polyacrylate (PAA), lithium montmorillonite powder, electrolyte salt zinc trifluoromethanesulfonate and water, and the mass ratio of the four is 1:2:45:52.
  • PAA polyacrylate
  • the composite three-layer membrane is dried in a tunnel furnace to obtain a three-layer prefabricated zinc salt membrane H, and then rolled up.
  • the temperature of the tunnel furnace is 80°C.
  • the ⁇ -MnO 2 dry electrode and zinc foil are used as positive and negative electrodes respectively, and the prefabricated zinc salt separator H is formed into a battery cell through a lamination process, and then loaded into an aluminum plastic film to make a reserve zinc-manganese secondary battery.
  • the battery is needed, 0.5 mol/L ZnSO 4 solution is injected into the battery, and the amount of ZnSO 4 solution injected is 10 mL/Ah. After the injection port is sealed, charging and discharging can be carried out.
  • Example 5 Prefabricated zinc salt diaphragm and prepared zinc-manganese secondary battery
  • the polyphenylene sulfide solid diaphragm A enters the laminating machine through the guide rail, and the upper supporting diaphragm B is dipped into the glue C through the glue tank where the glue C is stored, and the excess glue is scraped off by a scraper, and is compounded with the polyphenylene sulfide solid diaphragm A on the platform, and then the upper supporting diaphragm B and the solid diaphragm A are compounded by rolling.
  • the upper supporting diaphragm B is a hydrophilic polypropylene diaphragm (PP), and the glue C is composed of polytetrafluoroethylene (PTFE), zinc dihydrogen phosphate, electrolyte salt zinc sulfate and water, and the mass ratio of the four is 5:7:38:50.
  • the composite diaphragm is dried in a tunnel furnace and then cut to obtain a double-layer prefabricated zinc salt diaphragm D, and rolled up. The temperature of the tunnel furnace is 100°C.
  • the polyphenylene sulfide side of the double-layer prefabricated zinc salt diaphragm D is passed through the glue tank for storing the glue E to pick up the glue E, and the excess glue is scraped off by a scraper, and then compounded with the lower support membrane F on the platform, and then the lower support membrane F and the double-layer prefabricated zinc salt diaphragm D are compounded by rolling.
  • the support membrane F is a hydrophilic polyethylene film (PE)
  • the glue E is composed of polytetrafluoroethylene (PTFE), lithium-based montmorillonite powder, electrolyte salt zinc sulfate and water, and the mass ratio of the four is 5:7:38:50.
  • the three-layer diaphragm after compounding is dried in a tunnel furnace to obtain a three-layer prefabricated zinc salt diaphragm H, and then rolled up. The temperature of the tunnel furnace is 100°C.
  • LiMn 2 O 4 dry electrode and dry electrode made of zinc powder are used as positive and negative electrodes respectively and prefabricated zinc salt separator H is laminated to form a battery cell, which is then placed in an aluminum plastic film to form a zinc-manganese secondary battery.
  • water is injected into the battery at a rate of 8 mL/Ah. After the injection port is sealed, charging and discharging can be performed.
  • Example 6 Prefabricated zinc salt diaphragm and prepared zinc-manganese secondary battery
  • the polyphenylene sulfide solid diaphragm A enters the laminating machine through the guide rail, and the upper supporting diaphragm B passes through the glue tank where the glue C is stored to pick up the glue C, and the excess glue is scraped off by a scraper, and then composited with the polyphenylene sulfide solid diaphragm A on the platform, and then the composite of the upper supporting diaphragm B and the solid diaphragm A is completed by roller pressing.
  • the layer support membrane B is a hydrophilic polypropylene membrane (PP), and the glue C is composed of polytetrafluoroethylene (PTFE), zinc dihydrogen phosphate, electrolyte salt zinc sulfate and water, and the mass ratio of the four is 5:7:38:50.
  • the composite membrane is dried in a tunnel furnace and then cut to obtain a double-layer prefabricated zinc salt membrane D, which is then rolled up. The temperature of the tunnel furnace is 100°C.
  • the polyphenylene sulfide side of the double-layer prefabricated zinc salt diaphragm D is passed through the glue tank for storing the glue E to pick up the glue E, and the excess glue is scraped off by a scraper, and then compounded with the lower support membrane F on the platform, and then the lower support membrane F and the double-layer prefabricated zinc salt diaphragm D are compounded by rolling.
  • the support membrane F is a hydrophilic polyethylene film (PE)
  • the glue E is composed of polytetrafluoroethylene (PTFE), lithium-based montmorillonite powder, electrolyte salt zinc sulfate and water, and the mass ratio of the four is 5:7:38:50.
  • the three-layer diaphragm after compounding is dried in a tunnel furnace to obtain a three-layer prefabricated zinc salt diaphragm H, and then rolled up. The temperature of the tunnel furnace is 100°C.
  • LiMn 2 O 4 dry electrode and dry electrode made of zinc powder are used as positive and negative electrodes respectively and prefabricated zinc salt separator H are formed into a battery cell through a lamination process, and then loaded into an aluminum plastic film to make a reserve zinc-manganese secondary battery.
  • a 1 mol/L mixed solution of MgSO 4 and NaCl is injected into the battery, and the amount of the mixed solution injected is 7 mL/Ah. After the injection port is sealed, charging and discharging can be carried out.
  • Example 7 Prefabricated zinc salt diaphragm and zinc-manganese secondary battery
  • the polyphenylene sulfide solid diaphragm A enters the laminating machine through the guide rail, and the upper supporting diaphragm B is dipped into the glue C through the glue tank where the glue C is stored, and the excess glue is scraped off by a scraper, and is compounded with the polyphenylene sulfide solid diaphragm A on the platform, and then the upper supporting diaphragm B and the solid diaphragm A are compounded by rolling.
  • the upper supporting diaphragm B is a cellulose diaphragm
  • the glue C is composed of polytetrafluoroethylene (PTFE), zinc dihydrogen phosphate, electrolyte salt zinc sulfate and water, and the mass ratio of the four is 4:2:52:40.
  • the composite diaphragm is dried in a tunnel furnace and then cut to obtain a double-layer prefabricated zinc salt diaphragm D, which is then rolled up.
  • the temperature of the tunnel furnace is 85°C.
  • the polyphenylene sulfide side of the double-layer prefabricated zinc salt diaphragm D is passed through the glue tank for storing the glue E to pick up the glue E, and the excess glue is scraped off by a scraper, and then composited with the lower support membrane F on the platform, and then the composite of the lower support membrane F and the double-layer prefabricated zinc salt diaphragm D is completed by rolling.
  • the support membrane F is a cellulose diaphragm
  • the glue E is composed of polytetrafluoroethylene (PTFE), lithium-based montmorillonite powder, electrolyte salt zinc sulfate and water, and the mass ratio of the four is 4:2:52:40.
  • the composite three-layer diaphragm is dried in a tunnel furnace to obtain a three-layer prefabricated zinc salt diaphragm H, and then rolled up. The temperature of the tunnel furnace is 85°C.
  • LiMn 2 O 4 dry electrode and dry electrode made of zinc powder are used as positive and negative electrodes respectively and prefabricated zinc salt separator H is laminated to form a battery cell, which is then placed in an aluminum plastic film to form a zinc-manganese secondary battery.
  • a 1 mol/L mixed solution of Na 2 SO 4 and KCl is injected into the battery.
  • the amount of the mixed solution injected is It is 8mL/Ah. After sealing the liquid injection port, charging and discharging can be carried out.
  • Figure 10 is a comparison of the capacities of the zinc-manganese secondary battery of Example 3-7 after adding different electrolytes. It can be clearly seen that the addition of cations other than zinc ions to form a dual-ion and multi-ion system has a larger capacity and a higher energy density of the battery.
  • the zinc-manganese secondary battery in this embodiment uses ⁇ -MnO2 semi-dry positive electrode and zinc powder semi-dry negative electrode as electrodes, and uses the polyphenylene sulfide solid diaphragm made of polyphenylene sulfide powder after hydrothermal modification in Example 1 to make a prefabricated zinc salt diaphragm. After the electrode and the prefabricated zinc salt diaphragm material are stacked, the stainless steel current collector and the nickel pole ear are resistance welded. After the welding is completed, the welding point is protected with epoxy resin to achieve a water-blocking and insulating effect.
  • Figures 11 and 12 are respectively the laminated core packs of the zinc-manganese secondary battery before and after the welding point protection, and are packaged with aluminum-plastic film as the outer packaging material, as shown in Figure 13.
  • this embodiment also relates to a formation method of the zinc-manganese secondary battery prepared above, specifically: the battery is first injected with a 1 mol/L sodium sulfate aqueous solution, and the injection volume is 7 mL/Ah. A discharge is performed once with a small current of 10 mA/g, and after 3 cycles of charge and discharge with the small current, methanol is injected in the battery discharge state, and the volume ratio of the aqueous electrolyte to the alcohol is 5:0.7, and then vacuum packaging is performed.
  • Figure 14 is the charge and discharge curve of the zinc-manganese secondary battery prepared in this embodiment at 7°C after the formation system of first water and then alcohol.
  • the zinc-manganese secondary battery in this embodiment uses ⁇ -MnO2 semi-dry method positive electrode and zinc powder semi-dry method negative electrode as electrodes, and the polyphenylene sulfide solid diaphragm made of polyphenylene sulfide powder after hydrothermal modification in Example 2 is used to make a prefabricated zinc salt diaphragm.
  • the stainless steel current collector of the positive electrode and the nickel pole ear, and the copper current collector of the negative electrode and the copper pole ear are welded by resistance welding, and the welding points are protected by unsaturated polyester.
  • this embodiment also relates to a formation method of the zinc-manganese secondary battery prepared above, specifically: the battery is first injected with a 1 mol/L sodium chloride aqueous solution, and the injection volume is 8 mL/Ah. A discharge is performed once with a 20 mA/g low current formation, and after 10 cycles of low current charge and discharge, isopropanol is injected in the battery discharge state, and the volume ratio of the aqueous electrolyte to the alcohol is 5:2, and then vacuum packaging is performed.
  • Figure 15 is a stable cycle curve of the zinc-manganese secondary battery prepared in this embodiment after the formation system of first water and then alcohol.
  • the zinc-manganese secondary battery in this embodiment uses ⁇ -MnO2 semi-dry positive electrode and zinc powder semi-dry negative electrode as electrodes, and uses a polyphenylene sulfide solid diaphragm made of polyphenylene sulfide powder after hydrothermal modification to make a prefabricated zinc salt diaphragm.
  • the stainless steel current collector is welded to the titanium pole ear by resistance welding, and the welding points are protected by epoxy resin.
  • this embodiment also relates to a formation method of the zinc-manganese secondary battery prepared above, specifically: the battery is first injected with a 1 mol/L zinc sulfate aqueous solution, and the injection volume is 10 mL/Ah. A discharge is performed once with a 20 mA/g low current formation, and after 10 cycles of low current charge and discharge, ethylene glycol is injected in the battery discharge state, and the volume ratio of the aqueous solution electrolyte to the alcohol is 5:3, and then vacuum packaging is performed.
  • Figure 16 is a charge and discharge curve at 0°C of the remark zinc-manganese secondary battery prepared in this embodiment after the formation system of first water and then alcohol.
  • the remark zinc-manganese secondary battery in this embodiment uses a ⁇ -MnO2 semi-dry positive electrode, a zinc powder semi-dry negative electrode and a polyphenylene sulfide solid diaphragm made of polyphenylene sulfide powder after hydrothermal modification to make a prefabricated zinc salt diaphragm.
  • the stainless steel current collector of the positive electrode is welded to the nickel pole ear, and the copper current collector of the negative electrode is welded to the copper pole ear using resistance welding, and the welding points are protected by furan resin.
  • this embodiment also relates to a formation method of the zinc-manganese secondary battery prepared above, specifically: the battery is first injected with a 1 mol/L zinc trifluoromethanesulfonate aqueous solution, and the injection volume is 8 mL/Ah. A discharge is performed once with a 20 mA/g low current formation, and after 5 cycles of low current charge and discharge, isopropanol is injected in the battery discharge state, and the volume ratio of the aqueous solution electrolyte to the alcohol is 5:5, and then vacuum packaging is performed.
  • Figure 17 is the charge and discharge curve of the zinc-manganese secondary battery prepared in this embodiment at -10°C after the formation system of water first and then alcohol.
  • Example 12 Equipment and method for manufacturing polyphenylene sulfide solid diaphragm
  • This embodiment discloses a manufacturing device for a polyphenylene sulfide solid diaphragm, including a powder processing system, a high-speed shearing machine, a screw extruder, a horizontal cold roller press, and a horizontal hot roller press.
  • the powder processing system includes an air compressor, an air storage tank, a cold dryer, a drying adsorption tower, a purification column, an air preheating system, a powder heating system, a supersonic shear mixer, and a gas-solid separation tower that are connected in sequence.
  • FIG18 is a schematic diagram of the structure of the powder processing system described in this embodiment.
  • the supersonic shear mixer has a semi-enclosed cavity, and the air outlet of the purification column is connected to the air inlet of the semi-enclosed cavity of the supersonic shear mixer, and the air preheating system is arranged on the air pipeline between the purification column and the supersonic shear mixer.
  • the heating system is arranged at the discharge port of the semi-enclosed cavity of the supersonic shear mixer.
  • the discharge port of the semi-enclosed cavity of the supersonic shear mixer is connected to the gas-solid separation tower through a pipeline.
  • the gas-solid separation tower is provided with an air outlet at the top, a discharge port at the bottom, and an air hammer air inlet in the middle.
  • the gas source of the air hammer is the dry compressed air bypass after the purification column, and the air hammer function is realized by intermittently releasing compressed air.
  • the film-making flow process of the powder treated by the powder processing system is completed by the high-speed shearing machine, screw extruder, horizontal cold roller press, and horizontal hot roller press shown in Figure 19.
  • the powder treated by the powder processing system is sent to the high-speed shearing machine, and after shearing, it enters the screw extruder.
  • the horizontal cold roller press and the horizontal hot roller press are sequentially arranged downstream of the screw extruder, and a heating conveying guide rail is arranged between the horizontal cold roller press and the horizontal hot roller press.
  • This embodiment discloses a method for preparing a polyphenylene sulfide solid diaphragm using the polyphenylene sulfide solid diaphragm manufacturing device, and the specific steps are as follows:
  • LiCl solution 3 parts by mass of LiCl were dissolved in 12 parts by mass of deionized water to prepare a LiCl solution, 0.5 parts by mass of tetrachlorobenzoquinone and 10 parts by mass of cross-linked high-crystalline polyphenylene sulfide powder (crystallinity>70%) were mixed to prepare a mixed powder C, the LiCl solution and the mixed powder C were mixed to form a slurry D, the slurry D was loaded into a closed reactor for a hydrothermal reaction, the hydrothermal reaction atmosphere was air, the temperature was 210°C, the reaction time was 2 hours, the hydrothermal reaction filling rate was 30%, after the reaction was completed, the powder was washed and neutrally dried to prepare a powder E.
  • 6wt% polytetrafluoroethylene powder and 94wt% powder E are mixed in a mixer to form powder F.
  • the mixing process is carried out under the temperature condition that polytetrafluoroethylene is in a glassy state.
  • the dry adsorption process is to use two dry adsorption towers containing molecular sieves, with a total weight of 400kg. The two towers work and regenerate alternately, and the alternating time is 6 minutes.
  • the dry and purified gas After the dry and purified gas is preheated at 45°C, it passes through a nozzle and enters a semi-enclosed cavity, where it is accelerated to supersonic speed to form a supersonic jet H of extremely dry air with a dew point of -40°C.
  • Powder F is preheated at 100°C and added into the semi-enclosed cavity. It is sheared by friction of the supersonic jet H of extremely dry air.
  • the molecular chain of polytetrafluoroethylene in powder F is extended and opened, forming physical adhesion with the powder in F without chemical reaction, and powder I is obtained.
  • Powder I is blown into the solid-gas separation tower with the air flow. There is a dust removal filter inside the separation tower to separate the solid material and gas. The gas is discharged directly, and the powder adhering to the filter element is blown away by the air hammer.
  • the gas source of the air hammer is the purified dry compressed air bypass, and the air ham
  • the powder I is added to the high-speed shearing machine for secondary fiberization. After the material is discharged, it enters the screw extruder and extrudes 10 continuous thick strips J. The diameter of the thick strip J is 8 mm. It enters the horizontal cold roller press with a roller surface temperature of 20°C for primary thinning to 0.8 mm. After thinning, it enters the heated conveying guide rail at 130°C, and enters the horizontal hot roller press with a roller surface temperature of 130°C while heating and feeding. It is secondary thinned to 30 ⁇ m, and the two edges are cut off to make the finished solid diaphragm L, which is rolled up. The trimmed material K is recovered and added to the high-speed shearing machine for reuse.
  • Figure 20 is a surface SEM image of the solid diaphragm
  • Figure 21 is a cross-sectional SEM image of the solid diaphragm.
  • the solid diaphragm is a dense membrane composed of an entangled network structure formed by fibrous PTFE and plastically deformed PPS crystal particles.
  • the porosity is extremely low, and the integral calculation of the porosity in the figure is 3%.
  • 5wt% polytetrafluoroethylene powder and 95wt% powder E are mixed in a mixer to form powder F.
  • the mixing process is carried out under the temperature condition that polytetrafluoroethylene is in a glassy state.
  • the dry adsorption process is to use two dry adsorption towers containing molecular sieves, with a total weight of 500kg. The two towers work and regenerate alternately, and the alternating time is 8 minutes.
  • the dry and purified gas After the dry and purified gas is preheated at 50°C, it passes through a nozzle and enters a semi-enclosed cavity, where it is accelerated to supersonic speed to form a supersonic jet H of extremely dry air with a dew point of -45°C.
  • Powder F is preheated at 120°C and added into a semi-enclosed cavity, where it is frictionally sheared by a supersonic jet H of extremely dry air.
  • the molecular chains of polytetrafluoroethylene in powder F are stretched and opened, forming physical adhesion with the powder in F without chemical reaction, thereby obtaining powder I.
  • Powder I is blown into a solid-gas separation tower along with the air flow.
  • a dust removal filter is provided inside the separation tower to separate solid materials and gas.
  • the gas is discharged directly, and the adhered powder on the filter element is blown into the receiving barrel below by an air hammer.
  • the gas source of the air hammer is a purified dry compressed air bypass, and the air hammer function is realized by intermittently releasing compressed air.
  • the powder I is added to a high-speed shearing machine for secondary fiberization, and then discharged into a screw extruder.
  • the extrusion forms a continuous thick cake J with a diameter of 10 mm, and enters a horizontal cold roller press with a roller surface temperature of 10°C for primary thinning to 1 mm. After thinning, it enters a 130°C heated conveying guide rail, and while being heated and fed, it enters a horizontal hot roller press with a roller surface temperature of 120°C for secondary thinning to 35 ⁇ m, and the two edges are cut off to form a finished solid diaphragm L, which is then rolled up.
  • the trimmed material K is recovered and added to a high-speed shearing machine for reuse.
  • 4wt% polytetrafluoroethylene powder and 96wt% powder E are mixed evenly in a mixer to form powder F.
  • the mixing process is carried out under the temperature condition that polytetrafluoroethylene is in a glassy state.
  • the dry adsorption process is to use two dry adsorption towers containing molecular sieves, with a total weight of 1000kg. The two towers work and regenerate alternately, and the alternating time is 7 minutes.
  • the dry and purified gas After the dry and purified gas is preheated at 47°C, it passes through a nozzle and enters a semi-enclosed cavity, where it is accelerated to supersonic speed to form a supersonic jet H of extremely dry air with a dew point of -42°C.
  • Powder F is preheated at 125°C and added into a semi-enclosed cavity, where it is frictionally sheared by a supersonic jet H of extremely dry air.
  • the molecular chains of polytetrafluoroethylene in powder F are stretched and opened, forming physical adhesion with the powder in F without chemical reaction, thereby obtaining powder I.
  • Powder I is blown into a solid-gas separation tower along with the air flow.
  • a dust removal filter is provided inside the separation tower to separate solid materials and gas.
  • the gas is discharged directly, and the adhered powder on the filter element is blown into the receiving barrel below by an air hammer.
  • the gas source of the air hammer is a purified dry compressed air bypass, and the air hammer function is realized by intermittently releasing compressed air.
  • the powder I is added to a high-speed shearing machine for secondary fiberization. After being discharged, it enters a screw extruder and is extruded into a continuous thick cake J with a diameter of 7 mm. It enters a horizontal cold roller press with a roller surface temperature of 25°C for primary thinning to 0.8 mm. After thinning, it enters a 130°C heated conveying guide rail, and is fed while heated into a horizontal hot roller press with a roller surface temperature of 130°C for secondary thinning to 40 ⁇ m. The two edges are cut off to make a finished solid diaphragm L, which is then rolled up. The trimmed material K is recovered and added to the high-speed shearing machine for reuse.
  • MgCl2 3.5 parts by mass of MgCl2 are dissolved in 9 parts by mass of deionized water to prepare MgCl2 solution, 0.45 parts by mass of tetrachlorobenzoquinone and 11 parts by mass of cross-linked high-crystalline polyphenylene sulfide powder (crystallinity>60%) are mixed to prepare mixed powder C, the MgCl2 solution and mixed powder C are mixed into slurry D, the slurry D is loaded into a closed reactor for hydrothermal reaction, the hydrothermal reaction atmosphere is air, the temperature is 215°C, the reaction time is 3 hours, the hydrothermal reaction filling rate is 30%, after the reaction is completed, the powder is washed and neutrally dried to prepare powder E.
  • 4wt% polytetrafluoroethylene powder and 96wt% powder E are mixed evenly in a mixer to form powder F.
  • the mixing process is carried out under the temperature condition that polytetrafluoroethylene is in a glassy state.
  • the dry adsorption process is to use two dry adsorption towers containing molecular sieves, with a total weight of 600kg. The two towers work and regenerate alternately, and the alternating time is 8 minutes.
  • the dry and purified gas After the dry and purified gas is preheated at 45°C, it passes through a nozzle and enters a semi-enclosed cavity, where it is accelerated to supersonic speed to form a supersonic jet H of extremely dry air with a dew point of -40°C.
  • Powder F is preheated at 130°C and added into a semi-enclosed cavity, where it is frictionally sheared by a supersonic jet H of extremely dry air.
  • the molecular chains of polytetrafluoroethylene in powder F are stretched and opened, forming physical adhesion with the powder in F without chemical reaction, thereby obtaining powder I.
  • Powder I is blown into a solid-gas separation tower along with the air flow.
  • a dust removal filter is provided inside the separation tower to separate solid materials and gas.
  • the gas is discharged directly, and the adhered powder on the filter element is blown into the receiving barrel below by an air hammer.
  • the gas source of the air hammer is a purified dry compressed air bypass, and the air hammer function is realized by intermittently releasing compressed air.
  • the powder I is added to a high-speed shearing machine for secondary fiberization. After being discharged, it enters a screw extruder and is extruded into a continuous thick cake J with a diameter of 9 mm. It enters a horizontal cold roller press with a roller surface temperature of 15°C for primary thinning to 0.9 mm. After thinning, it enters a 130°C heated conveying guide rail, and is fed while heated into a horizontal hot roller press with a roller surface temperature of 130°C for secondary thinning to 40 ⁇ m. The two edges are cut off to make a finished solid diaphragm L, which is then rolled up. The trimmed material K is recovered and added to the high-speed shearing machine for reuse.
  • Example 17 Method for manufacturing a manganese oxide positive electrode
  • manganese dioxide is mixed with polytetrafluoroethylene, and then dry supersonic jet gas is used to open the molecular chain of polytetrafluoroethylene and physically adhere to the positive electrode material powder below the glass transition temperature of polytetrafluoroethylene. Then, an alcohol solution is sprayed on the fiberized powder, and after banburying, shearing and granulation, hot roller pressing is performed to form a positive electrode membrane.
  • the multilayer positive electrode film is then composited into a composite positive electrode self-supporting film with a thickness of 100-150 ⁇ m through multiple cold rolling presses. Finally, the composite positive electrode self-supporting film is composited with a sandblasted stainless steel foil with a glue-coated surface through a hot rolling press.
  • Example 18 Method for manufacturing a zinc negative electrode
  • Zinc powder, ECP, high-purity graphite, montmorillonite powder, and indium chloride are mixed in a mixer at a ratio of 74wt%: 7wt%: 5wt%: 5wt%: 1wt% to obtain powder A; 8wt% polytetrafluoroethylene powder and 92wt% powder A are mixed in a mixer at 0°C to obtain powder B; material B is added with a mixed solvent prepared by ethanol and deionized water in a volume ratio of 1:1 in a planetary ball mill, and the ball mill beads are rotated at a high speed in a wet state, and the PTFE wire drawing is continuously rubbed to form a mesh structure, and indium chloride reacts with zinc powder by reduction reaction.
  • micelle C is filtered to obtain a uniform micelle; the micelle C is kneaded to form a uniform micelle, and the micelle is sheared and granulated to form a millimeter-level particle material E with a uniform size and a solid content of 50%; the particles E are rolled once by a horizontal hot roller press to obtain a 150 ⁇ m negative electrode film F, and the hot rolling temperature is 80°C.
  • the negative electrode membrane F is trimmed under the horizontal hot roller to meet the membrane width requirements. The trimmed material can be shredded again and put into the granular material E to complete the recycling of the edge material.
  • the trimmed negative electrode membrane F is attached to the support belt of the porous release paper to complete the winding.
  • the whole roll After winding, the whole roll is dried to remove part of the solvent.
  • the solid content of the negative electrode membrane F in the semi-dry state is 65%.
  • the surface and cross-sectional structures of the negative electrode membrane F are shown in Figures 22 and 23.
  • the entangled network structure formed by PTFE can make the structure of the electrode more stable.
  • the semi-dried negative electrode membrane F after the release paper is removed is thermally composited on both sides of the coated stainless steel foil to form an electrode.
  • Example 19 Method for manufacturing a zinc negative electrode
  • Zinc powder, SP, high-purity graphite, illite powder and cupric chloride are mixed in a mixer according to 50wt%:15wt%:15wt%:10wt%:2wt% to obtain powder A; 8wt% polytetrafluoroethylene powder and 92wt% powder A are mixed in a mixer at 5°C to obtain powder B; a certain amount of alcohol solvent is added to material B in a planetary ball mill, and the material B is subjected to high-speed rotation of ball mill beads in a wet state, and continuous friction causes the material to be drawn into a mesh structure, the molecular chain of polytetrafluoroethylene in powder B is extended and opened, and forms physical adhesion with the powder in A, and cupric chloride and zinc powder undergo reduction reaction, and after the above process is completed, micelle C is filtered to obtain micelle C; micelle C is kneaded to form a uniform micelle, and the micelle is sheared and granulated to form
  • the negative electrode film F is trimmed under the horizontal hot roller to meet the film width requirements.
  • the trimmed material can be shredded again and put into the granular material E to complete the recycling of the trimmed material.
  • the negative electrode film F is pasted on the support belt of the porous release paper to complete the winding. After winding, the whole roll is dried to remove part of the solvent.
  • the solid content of the semi-dried negative electrode film F is 60%.
  • the semi-dried negative electrode film F after the release paper is peeled off is thermally laminated on both sides of the coated stainless steel foil to form an electrode using a hot pressing composite process.
  • Example 20 Method for manufacturing a zinc negative electrode
  • Zinc powder, ECP, artificial graphite, kaolin, and indium sulfate are mixed in a mixer according to 60wt%:10wt%:8wt%:10wt%:4wt% to obtain powder A; 8wt% polytetrafluoroethylene powder and 92wt% powder A are mixed in a mixer at 5°C to obtain powder B; a certain amount of alcohol solvent is added to powder B in a planetary ball mill, and the powder B is subjected to high-speed rotation of ball mill beads in a wet state, and continuous friction causes the powder to be drawn into a mesh structure, the molecular chain of polytetrafluoroethylene in powder B is extended and opened, and forms physical adhesion with the powder in A, and indium sulfate and zinc powder undergo reduction reaction, and after the above process is completed, micelle C is filtered to obtain micelle C; micelle C is kneaded to form a uniform micelle, and the micelle is sheared and granul
  • the negative electrode film F is trimmed under the horizontal hot roller to meet the film width requirements.
  • the trimmed material can be shredded again and put into the granular material E to complete the recycling of the edge material.
  • the trimmed negative electrode film F is attached to the support belt of the porous release paper to complete the winding. After winding, the whole roll is dried to remove part of the solvent.
  • the solid content of the semi-dried negative electrode film F is 60%.
  • the semi-dried negative electrode film F after the release paper is peeled off is thermally laminated on both sides of the coated stainless steel foil to form an electrode using a hot pressing composite process.
  • Example 21 Method for manufacturing a zinc negative electrode
  • Zinc powder, SP, artificial graphite, halloysite powder and copper sulfate are mixed in a mixer according to 67wt%: 5wt%: 5wt%: 10wt%: 5wt% to obtain powder A; 8wt% polytetrafluoroethylene powder and 92wt% powder A are mixed in a mixer at 0°C to obtain powder B; a certain amount of alcohol solvent is added to material B in a planetary ball mill, and the material B is subjected to high-speed rotation of ball mill beads in a wet state, and continuous friction causes the material to be drawn into a mesh structure, the molecular chain of polytetrafluoroethylene in powder B is extended and opened, and forms physical adhesion with the powder in A, and copper sulfate and zinc powder undergo reduction reaction, and after the above process is completed, micelle C is filtered to obtain micelle C; micelle C is kneaded to form a uniform micelle, and the micelle is sheared and granul
  • the negative electrode film F is trimmed under the horizontal hot roller to meet the film width requirements.
  • the trimmed material can be shredded again and put into the granular material E to complete the recycling of the edge material.
  • the trimmed negative electrode film F is attached to the porous release paper support belt to complete the winding. After winding, the whole roll is dried and removed. Part of the solvent, the solid content of the negative electrode film F in the semi-dried state is 55%.
  • the semi-dried negative electrode film F after the release paper is peeled off is thermally laminated on both sides of the glue-coated stainless steel foil to form an electrode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)
  • Cell Separators (AREA)

Abstract

本发明提供了一种改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、化成及应用方法。通过水热合成对聚苯硫醚粉体中的四氯对苯醌进行减氯加氢反应，生成氯儿茶酚结构分子，改善聚苯硫醚基固态隔膜对有害分子的吸附性能，同时结合电池装配过程中保护焊点，以及化成过程中采用先注水溶液电解液后加醇的化成方法，提高电池循环稳定性并拓宽电池的服役温度区间。预制锌盐隔膜在制造过程中将电解质锌盐预制到固态隔膜与上下支撑隔膜的复合胶液之中，解决了锌锰二次电池中高浓度电解液难以均匀浸润到电池极片内部的问题，提高了锌锰二次电池对的生产效率和电池性能。

Description

改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法 技术领域
本发明属于二次电池技术领域，具体涉及一种改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法。
背景技术
水系锌锰电池二次电池具有安全环保、资源丰富、成本低廉等优点，近年来受到了研究者的广泛关注。安时级的商用化水系锌锰二次电池由于寿命短、低温性能差，很难应用推广，现有的改进方法是在水系电解液中加入低温添加剂的方法，包括醇类、PEG、PVA等，形成共晶溶液，有效降低电解液的凝固点，从而开发低温锌锰二次电池。然而，加入添加剂后，却会增加副反应机会，特别是在最初的化成循环中，可以明显观察到容量的大幅衰减，这是由于副反应产生的有害成分，在正负极间穿梭，相互恶化导致的，需要进一步改进。另外，专利ZL202110122474.3中提到采用四氯对苯醌作为阴离子吸附剂，同有害成分形成偶极吸附，提高隔膜的阳离子迁移数，可以有效抑制副反应的产生，然而四氯对苯醌中含氯较高，长时间循环，氯离子会导致集流体腐蚀失效。
目前水系电池电极生产工艺普遍采用湿法涂布制作，专利202211223026.3和专利202210355256.9提出了采用半干法的工艺制造锌锰二次电池的电极，采用锌锰二次电池采用干法电极制造工艺，虽然可以有效避免湿法涂布过程中浆料不均一、粘度控制困难、溶剂去除复杂、电极组份分层和极片掉粉等一系列问题，但同时也带来了挑战，比如干法电极的孔隙率较低，小于30％，导致注液效率低。特别是锌锰二次电池电解液的浓度高(>2mol/L)，粘度非常大，很难实现均匀浸润，导致电解质在电池极片和隔膜中的分布非常不均匀。为了解决这个问题，一般都会通过增加浸润时间和提高搁置温度来提升电池的浸润效果，但这无疑会浪费大量时间和电能，大大降低电池的生产效率。
同时，在电化学储能领域，电池能长期且有效存放以及能安全的运输也是亟待解决的问题。现有的存储方式通常提前将电解液注入电池，这给运输和存储过 程带来了安全隐患。随着存储时间的延长，电池中的电解液会分解，电池的容量会大幅衰减，甚至可能导致电池短路，造成资源浪费。
中国发明专利202110380015.5和专利申请202210444350.1提供了基于聚苯硫醚固态隔膜的三明治结构复合隔膜，该隔膜结构虽然可以有效避免枝晶，但依然无法解决水系隔膜的浸润问题，导致安时级锌锰二次电池内部锌盐分布不均匀，电池一致性差。
因此，需要研发一种新型的隔膜和二次电池，以解决上述问题。
发明内容
一方面，为了解决安时级的商用化水系锌锰二次电池寿命短、低温性能差的问题，本发明提供了一种适用于长寿命宽温区安时级锌锰二次电池的改性聚苯硫醚及其制造方法。通过水热合成对聚苯硫醚粉体中的四氯对苯醌进行减氯加氢反应，生成氯儿茶酚结构分子，改善聚苯硫醚基固态隔膜对有害分子的吸附性能，同时结合电池装配过程中保护焊点，以及化成过程中采用先注水溶液电解液后加醇的化成方法，提高电池循环稳定性并拓宽电池的服役温度区间，提高电池耐低温性能。
一种适用于长寿命宽温区安时级锌锰二次电池固态隔膜的聚苯硫醚改性方法，其特征在于：将聚苯硫醚粉料、四氯对苯醌和去离子水按照10:0.25-0.75:1-12的质量比混合后，于180-240℃进行水热反应，在水热反应过程中四氯对苯醌分子发生了氯离子去除，羟基增加的反应，生成了氯儿茶酚类结构的分子。
进一步地，所述水热反应温的恒温时间为1-4小时，反应气氛为空气、氧气、氮气或氩气。
所述聚苯硫醚改性方法制成的改性聚苯硫醚，其特征在于，在聚苯硫醚固态隔膜中负载有氯儿茶酚类结构的分子；所述的氯儿茶酚类结构分子为2,5-二氯对苯二酚、2,3,5,6-四氯酚、3,4,5-三氯邻苯二酚、四氯氢醌、3,4,6-三氯邻苯二酚等一种或几种的混合物。
由所述改性聚苯硫醚制成的聚苯硫醚固态隔膜。
进一步地，所述改性聚苯硫醚制成的聚苯硫醚固态隔膜具有锌离子选择透过性。
另一方面，本发明还提出了一种预制锌盐隔膜、备注锌锰二次电池及其制造 方法。所述预制锌盐隔膜在制造过程中，将电解质锌盐预制到固态隔膜与上下支撑隔膜的复合胶液之中，解决了锌锰二次电池中高浓度电解液难以均匀浸润到电池极片内部的问题，同时还能够制成一种在存储和运输过程中不需要加注电解液的备注锌锰二次电池，提高了锌锰二次电池对的生产效率和电池性能。
预制锌盐隔膜的制造方法，其特征在于，包括以下步骤：
(1)将聚苯硫醚固态隔膜A、上层支撑隔膜B中的一个在沾取或者涂覆胶液C后将两者贴合，使胶液C位于聚苯硫醚固态隔膜A与上层支撑隔膜B之间，再经过辊压使上层支撑隔膜B与固态隔膜A的复合；复合后的上层支撑隔膜B与固态隔膜A经过烘干后制得双层预制锌盐隔膜D；
(2)将双层预制锌盐隔膜D的聚苯硫醚固态隔膜A裸露表面、下层支撑膜F中的一个在沾取或者涂覆胶液E后将两者贴合，使胶液E位于，经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，或者将胶液E聚苯硫醚固态隔膜A与下层支撑膜F之间，再经过辊压使下层支撑隔膜F与双层预制锌盐隔膜D的复合，复合后的三层隔膜经烘干后制得预制锌盐隔膜H；
所述上层支撑隔膜B和下层支撑隔膜F均为多孔隔膜，所述胶液C和胶液E为有机粘接剂和/或无机粘接剂与电解质锌盐、溶剂的混合物。
进一步地，所述有机粘接剂、无机粘接剂和电解质盐和溶剂的质量比为0-10：0-10：10-80：10-80。
进一步地，所述有机粘接剂为聚乙烯醇(PVA)、聚丙烯酸酯(PAA)、聚四氟乙烯(PTFE)中的一种或多种的混合物；无机粘接剂为钠基膨润土、磷酸二氢锌、锂基蒙脱石粉中的一种或多种的混合物；电解质锌盐为三氟甲烷磺酸锌、硫酸锌、氯化锌、高氯酸锌中的一种或几种的混合物；溶剂为去离子水、氮甲基吡咯烷酮(NMP)、酒精、丙二醇的一种或几种的混合物。
进一步地，所述聚苯硫醚固态隔膜A的厚度为5-60μm，所述多孔隔膜为聚乙烯隔膜(PE)、聚丙烯隔膜(PP)、纤维素膜、无纺布膜、PET膜中的一种，其厚度为3-30μm。
进一步地，所述胶液C、胶液E的用量为5-30mg/cm2；两次的烘干温度均为50-100℃；烘干后，干胶单层负载为2-15mg/cm2，所述预制锌盐隔膜H的厚度为70-200μm。
所述预制锌盐隔膜的制造方法制成的预制锌盐隔膜，其特征在于，包括聚苯硫醚固态隔膜A和位于聚苯硫醚固态隔膜A两侧的上支撑隔膜B、下支撑隔膜F，在上支撑隔膜B、下支撑隔膜F与聚苯硫醚固态隔膜A之间分别填充有包括有机粘接剂和/或无机粘接剂与电解质盐混合而成的混合物，固含量的质量比例为0-10：0-10：10-80：10-80。
进一步地，所述聚苯硫醚固态隔膜A中是由所述改性聚苯硫醚制成。
进一步地，所述聚苯硫醚固态隔膜A的制造设备，包括粉料处理系统、高速剪切机、螺杆挤出机、卧式冷辊压机、卧式热辊压机；
所述粉料处理系统包括依次连通的空压机、储气罐、冷干机、干燥吸附塔、净化柱，以及空气预热系统、粉料加热系统、超音速剪切混料机、气固分离塔；超音速剪切混料机具有半封闭型腔，所述净化柱的出气口与超音速剪切混料机的半封闭型腔的进气口连通，且空气预热系统设置在净化柱与超音速剪切混料机之间的空气管路上；所述粉料加热系统设置在超音速剪切混料机半封闭型腔的下料口处；所述超音速剪切混料机半封闭型腔的出料口通过管道与气固分离塔连通，气固分离塔的上部设有出气口、底部设有出料口、中部设有气锤进气孔；
经粉料处理系统处理的粉料被送入高速剪切机，经剪切后进入螺杆挤出机，所述卧式冷辊压机、卧式热辊压机依次设置在螺杆挤出机的下游，且卧式冷辊压机与卧式热辊压机之间设置加热输送导轨。
进一步地，所述干燥吸附塔的数量为多个，多个干燥吸附塔并联设置，分别与冷干机出气口、净化柱进气口连通；所述气锤的气体来源为净化柱后的干燥压缩空气旁路，通过间歇式释放压缩空气实现气锤功能。
进一步地，所述聚苯硫醚固态隔膜A的制造方法，包括以下步骤：
(1)制粉：
将金属氯化物A溶解在去离子水中制成溶液B，四氯对苯醌与聚苯硫醚粉料混合制成混合粉体C，将溶液B与混合粉体C混合成浆料D，浆料D装入密闭反应釜中，进行水热反应，反应结束后粉料清洗呈中性烘干，制成粉料E；
(2)纤维化：
将聚四氟乙烯粉体和粉料E在混料机中混合均匀至粉料F，混合过程在聚四氟乙烯呈玻璃态的温度条件下进行；
干燥的空气G经过空压机压缩、冷干、干燥吸附、净化、预热后，通过喷管，进入半封闭型腔，被加速到超音速，形成极干燥空气的超音速射流H；
粉料F经过预热加入到半封闭型腔中，被极干燥空气的超音速射流H摩擦剪切，粉料F中的聚四氟乙烯的分子链延展打开，同F中的粉体形成物理粘连，且不发生化学反应，获得粉料I；
粉料I随气流被吹入固气分离塔中，分离塔内部有除尘滤芯，用以分离固体粉料和气体，气体直接排出，滤芯上粘附的粉料被气锤吹震到下方的收料桶里；
(3)制膜：
粉料I加入到高速剪切机中，进行二次纤维化，出料后进入到螺杆挤出机中，挤出呈多条连续的粗条或连续厚饼J，并进入到卧式冷辊压机进行一次减薄，减薄后进入到加热输送导轨中，边加热边上料进入到卧式热辊压机中，进行二次减薄，并切去两边缘，制成成品的固态隔膜L，并收卷。
进一步地，所述制粉工艺中的所述金属氯化物A为氯化锂、氯化钠、氯化锌、氯化镁、氯化铝中的一种或几种的混合物；所述的聚苯硫醚粉料为交联态高结晶聚苯硫醚粉料，结晶度>60％，粉料的D50为3-25μm；所述的金属氯化物，去离子水，四氯对苯醌，聚苯硫醚的质量比为0-3:3-30:0.1-0.75:5-15；所述的水热反应釜内的气氛为空气或氩气，所述水热反应温度为150-250℃，所述水热反应时间为1-4小时；水热反应的体积填充率为20％-70％。
进一步地，所述纤维化过程中，干燥空气G，其室温25℃下相对湿度(RH)<10％；所述的空压机的功率大于等于15kW，连续化生产优选30kW以上；所述的极干燥空气的超音速射流H，其露点低于-40℃；所述干燥吸附过程为，采用多个内含分子筛的干燥吸附塔，分子筛总重>200kg，多个干燥吸附塔交替工作和再生，交替时间为3-12分钟。
进一步地，所述纤维化过程中，进入喷管前的空气预热温度为30-60℃，进入半封闭型腔中粉料F的预热温度为40-220℃。
进一步地，所述制膜过程，多条连续的粗条或连续厚饼J，其形状由螺杆挤出机挤压头模具决定，连续粗条的直径或连续厚饼的厚度在3-12mm之间；所述卧式冷辊压机的辊面温度为-10-30℃；所述一次减薄后的厚度为0.3-1.5mm；所述加热输送导轨的温度为90-150℃；所述卧式热辊压机的辊面温度为 110-160℃；所述二次减薄后的厚度为5-60μm。
由所述预制锌盐隔膜制成的备注锌锰二次电池制造方法，其特征在于，将预制锌盐隔膜H置于锰氧化物正极电极和锌负极电极之间，并进行极耳焊接，通过采用叠片机或卷绕机制备得到电池电芯，放入电池壳体或铝塑膜袋内，封装备用，储存；所述电池壳体或铝塑膜袋上留有能够密封的注液口。
进一步地，所述锰氧化物正极电极为采用半干法技术制造的二氧化锰干法电极，所述的锰氧化物为α-MnO2、β-MnO2、γ-MnO2、δ-MnO2、Mn2O3、Mn3O4、LiMn2O4中的一种或几种的混合物；所述锌负极电极为采用半干法技术制造的锌粉干法电极、锌箔、镀锌铜箔中的一种。
进一步地，在极耳焊接完成后对焊接点进行阻水绝缘保护。
进一步地，焊接点的阻水绝缘保护是采用阻水绝缘胶带包裹、涂氧化铝层或涂抹树脂保护；所述树脂为环氧树脂、酚醛树脂、呋喃树脂、不饱和聚酯中的一种或几种；所述极耳为镍极耳、铜极耳、钛极耳或钼极耳。
进一步地，在得到电池电芯后还需要采用外部加持机构以增大所述预制锌盐隔膜H、锰氧化物正极电极和锌负极电极间的预紧力，减小极间距，使极间距被控制在50-120μm。
进一步地，所述电池壳体外包装采用阻水阻气耐酸蚀材料，所述阻水阻气耐酸蚀材料为无孔膜。
进一步地，所述无孔膜优选为双向拉伸聚丙烯薄膜(BOPP)、流延聚丙烯薄膜(CPP)、聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)、聚丙烯(PP)无孔膜中的一种或几种的复合膜。
进一步地，所述锰氧化物正极电极的制造方法，包括以下步骤：首先将二氧化锰与聚四氟乙烯混合后，在聚四氟乙烯的玻璃化转变温度以下，采用干燥的超音速射流气体喷射使聚四氟乙烯的分子链打开与正极材料粉末物理粘连，再纤维化的粉料中喷洒醇溶液，经过密炼、剪切造粒后热辊压为正极膜，再经多次冷辊压将多层正极膜复合成厚度为100-150μm的复合正极自支撑膜，最后将复合正极自支撑膜与表面涂过胶的喷砂不锈钢箔通过热辊压机复合在一起。
进一步地，所述锌负极电极的制造方法，包括以下步骤：
将锌粉、导电剂、增韧导电剂、阳离子缓释剂、析氢抑制剂在混料机中混合 均匀至粉料A；
将聚四氟乙烯粉体和粉料A在混料机中混合均匀至粉料B；混合过程在聚四氟乙烯(PTFE)呈玻璃态的温度条件下进行；
所述粉料B和醇水混合溶剂在球磨设备中，通过球磨珠在高速转动中不断摩擦使得PTFE拉丝呈网状结构，粉料B中的聚四氟乙烯的分子链延展打开，同粉料A中的粉体形成物理粘连，析氢抑制剂与锌粉表面发生还原反应，待上述过程结束后，过滤获得胶团C；
胶团C经密炼后形成均匀胶团，再经过剪切造粒后制成大小均一的毫米级颗粒料E；
颗粒料E经卧式热辊压机热压制成负极膜F，并采用多孔离型纸做支撑托带完成收卷，贴覆离型纸的负极膜F整卷进行干燥，排除部分溶剂；
采用热压复合工艺，将揭掉离型纸后的半干燥负极膜F热复合在涂胶不锈钢箔的两面制成电极；
进一步地，述锌粉为粒径在5-20μm的粉末状颗粒；所述导电剂为super-P、ECP中的一种或两种，所述的增韧导电剂为人造石墨、高纯石墨中的一种或两种的混合物；所述的阳离子缓释剂为具有电负性且遇水体积膨胀的无机粉料；所述的析氢抑制剂是同锌粉在醇水溶剂中能发生还原反应的金属化合物；锌粉、导电剂、增韧导电剂、阳离子缓释剂、聚四氟乙烯、析氢抑制剂粉体的重量百分比:60％-90％：1％-10％：1％-10％：1％-10％：3％-15％：0.1％-5％。
进一步地，所述阳离子缓释剂为膨润土、蒙脱石粉、伊利石粉、高岭土粉、埃洛石粉中的一种或几种；所述析氢抑制剂为氯化铟、氯化铜、硫酸铟、硫酸铜中的一种或几种。
进一步地，所述醇水混合溶剂为水和异丙醇、丙二醇或乙醇的混合溶剂，水与醇的体积百分比为：40％-80％：20％-60％；所述的均匀胶团的固含量为40％-60％。
进一步地，所述颗粒料E经卧式热辊压机辊压一次达到负极膜F的厚度为90-200μm，热辊压温度为55-95℃。
进一步地，半干燥负极膜F与不锈钢箔热复合时，涂胶不锈钢箔被两张已揭掉离型纸的负极膜F夹在中间，经同速放卷，进入两个相对转动的卧式热辊压机， 辊压温度为30-120℃，通过调节辊缝宽度，控制压力，使得负极膜F刚好能够复合在涂胶不锈钢箔上即可，避免因辊压力过大导致负极膜F形变过大拉断不锈钢箔.
进一步地，所述的涂胶不锈钢箔为采用凹版印刷机将高导电浆料印刷在不锈钢箔的两面，不锈钢箔表面在涂胶前需经过喷砂处理，除掉表面轧制油，高导电浆料由高纯石墨、不亲水粘接剂和非水溶剂组成。
所述备注锌锰二次电池制造方法制成的备注锌锰二次电池，其特征在于，由锰氧化物正极电极、锌负极电极、三层预制锌盐隔膜H和带有可密封注液口的电池壳体或铝塑膜袋组成，锰氧化物正极电极、锌负极电极和三层预制锌盐隔膜H经极耳焊接后，置于电池壳体或铝塑膜袋内。
所述备注锌锰二次电池的应用方法，其特征在于，所述备注锌锰二次电池在存储运输过程中，不需要注液；在投入使用前，在电池中注入纯水、海水或稀电解液；优选地，所述的稀电解液为浓度为0.01mol/L到1mol/L的硫酸锌、硫酸钠、硫酸镁、氯化钠、三氟甲烷磺酸锌中的一种或几种的盐溶液，其溶剂为水、乙醇、甲醇、丙二醇、异丙醇、丙三醇中的一种或几种的混合物；优选地，注入液体的量为1-20mL/Ah。
所述备注锌锰二次电池的化成方法，其特征在于，在电池化成过程中，首先在所述二次电池中注入仅以水为溶剂的电解液，以电流密度为1-20mA/g的小电流化成进行一次放电，再进行充放电0-40圈后，在电池放电状态下，注入有机溶剂，再进行真空封装，所述有机溶剂为与水混合后能够降低水的凝固点的有机溶剂，所述的水溶液电解液和有机溶剂的体积比为5:0.3-5。
进一步地，所述以水为溶剂的电解液是2-3mol/L的三氟甲磺酸锌水溶液、2-3mol/L的硫酸锌水溶液或2-3mol/L的氯化锌水溶液；注液量为3-10mL/Ah。
进一步地，所述有机溶剂为醇、二甲基亚砜、碳酸丙烯酯、乙腈。
进一步地，所述的醇为甲醇、异丙醇、乙二醇、丙二醇、丙三醇中的一种或几种的混合醇。
本发明的有益效果如下：
本发明所述的预制锌盐隔膜的制造方法，在隔膜制造过程中将电解质锌盐预制到固态隔膜与上下支撑隔膜的复合胶液之中，制成预制锌盐的复合隔膜，使得 由所述预制锌盐隔膜制成的锌锰二次电池在存储、运输期间无需注入电解液的优点。在所述锌锰二次电池投入使用时，只需向电池中注入纯水、海水或低粘度的稀电解液，不仅能有效解决了锌锰二次电池制造过程中高浓度电解液难以均匀浸润到电池极片内部的问题，提高了电池性能，而且简化了二次电池的制造步骤和生产效率，提高了储运性能。
此外，备注锌锰二次电池在使用时，只需要向电池壳体或铝塑膜袋中加注能够形成水系电解液环境的液体，即可保证锌锰二次电池的正常充放电。所加入的溶液具有广泛的选择性，水、含锌的溶液，也可以是不同阳离子的溶液，如海水等，构成双阳离子或多阳离子体系，正极反应多样化。如加入纯水，预制锌盐隔膜中的锌离子溶出，此时电解液中仅含有锌离子，锰氧化物正极表面发生的是含锌锰氧化物的溶解\沉积反应；如加入海水，预制锌盐隔膜中的锌离子溶出和加入海水中的钠离子、镁离子构成多离子体系，较小的钠离子会嵌入到锰氧化物中去，正极中离子嵌入\脱出机制和溶解\沉积机制共存可以大幅提高水系二次电池的容量。另外，多阳离子体系还可以改善锌沉积动力学，有效避免枝晶，提高体系的循环稳定性。
与现有技术相比，本发明所述的预制锌盐隔膜和备注锌锰二次电池具有以下优势：
(1)通过预先加入电解质盐，确保其在电池内部均匀分布，有效防止枝晶在特定区域的过度生长。
(2)显著提升了电池的注液效率和整体生产效率。
(3)有效避免锌锰二次电池在循环过程中电解质盐的析出，从而延长了电池的循环寿命；提高了电池的存储寿命。
本发明所述适用于长寿命宽温区安时级锌锰二次电池的改性聚苯硫醚的制造方法，采用简便的水热合成方法，以廉价的去离子水作为提供质子的反应物，在水热反应过程中，四氯对苯醌脱去部分氯离子，醌基加氢变成羟基，形成更容易跟阴离子结合的吸电子集团，生成的氯儿茶酚结构更容易跟阴离子、氟化物、氯化物、氢化物等发生偶极吸附，从而断绝了锌锰二次电池正负极之间有害分子的穿梭，大幅提高聚苯硫醚固态隔膜的离子迁移数。另外生成的氯儿茶酚有更低的熔点，可以帮助聚苯硫醚隔膜在100到200℃的加工温度下软化，形成更薄， 表面更光滑的无孔固态隔膜。
本发明所述的聚苯硫醚固态隔膜制造过程中，所述纤维化过程采用的空气源为干燥的大气环境空气，其室温25℃下相对湿度(RH)<10％，其目的是通过产线的冷干和干燥吸附步骤后可以达到-40℃露点的极干空气，最大限度降低空气干燥过程中消耗的能源。获得极干空气的目的是能够让PTFE更好的纤维化，防止经过剪切摩擦后的PTFE纤维静电高导致的吸潮，使得后续的压膜产生断带。并且本发明中首先采用卧式冷辊压机对连续的粗条或连续厚饼进行一次减薄，此时的温度需要在PPS软化温度(130℃)以下，其目的只是为了控制后续热辊压的进料均匀。采用加热输送导轨的目的是将一次减薄后的连续薄饼(0.3-1.5mm)加热到PPS的变形温度以上，经过卧式热辊压机后，PPS晶体颗粒发生热塑性变形，可以更好的压成薄膜。本发明中热压后的薄膜两边切齐后，切边料可以回用到高速剪切机中，使得粉料的利用率达到100％，进一步降低成本。所制备的聚苯硫醚固态隔膜具有以下特点：孔隙率低；电导率高；离子迁移数高；离子选择性强；离子整流作用明显，有效抑制金属负极枝晶。
本发明的正负极采用半干法制备，正负极的粉体被纤维化的PTFE缠结捆扎，在充放电的过程中，正负极材料的溶出/沉积不会导致电极粉化。半干法锌粉负极制备过程中，锌粉表面通过化镀铟、化镀铜、醋酸化或磷酸化处理，有效抑制了锌粉的析氢。半干法锌负极中加入阳离子螯合剂等来稳定电解液中离子浓度变化，从而获得更稳定的循环。并且在半干法锌负极中引入膨润土、蒙脱石粉、伊利石粉、高岭土粉、埃洛石粉等无机粉料，遇水后体积膨胀几倍到几十倍，并有效固定水分，降低胶团的固含量，并防止胶团因溶剂量过多导致在后续压膜过程中粘辊，成膜后干燥过程中，无机粉料体积收缩，引入孔道，提高了半干法电极的孔隙率。膨润土、蒙脱石粉、伊利石粉、高岭土粉、埃洛石粉等无机粉料具有较强的电负性，通过层状晶体结构有效吸收电解液中过量的阳离子(Mn2+，H+，Zn2+)，起到阳离子缓释的作用，减缓因活性物质溶出/沉积导致的电解液中阳离子(Mn2+，H+，Zn2+)大幅波动，稳定电解液pH值，提供体系的高可逆性。并且本发明在球磨纤维化的过程中直接引入析氢抑制剂，浆料球磨的同时，析氢抑制剂与锌粉表面发生充分的还原反应，充分钝化锌粉表面，确保在制成电极后有效抑制析氢。另外，PTFE缠结网络的疏水作用也可以对锌粉起到保护作用。使 所述锌负极电极具有以下特点：(1)可以有效抑制枝晶；(2)具备阳离子缓释作用；(3)优良的三维导电网络，剥离/沉积活性位点多；(4)PTFE缠结网络结构稳定；(5)孔隙率大(6)可以有效避免锌负极析氢。
另外，本发明在所述锌锰二次电池的装配过程中，对焊点进行阻水绝缘保护措施，在锌锰二次电池循环的过程中非常重要，焊点如果跟电解液接触，充放电过程中，非常容易发生电化学腐蚀，从而导致电池能量效率低，甚至出现断路失效的现象。增设外部加持机构来缩小极间距，加强极片间紧密贴合，避免了因极间距过大，造成的析氢和析氧的副反应。极大避免了电池在充放电过程中的副反应的发生，从而保证电池的循环稳定性，大幅提高电池的电化学性能；在不影响电池容量、倍率性能和能量密度的基础上，拓宽了电池的服役温度。
本发明采用涂胶喷砂不锈钢，喷砂后的不锈钢，表面除掉了轧制油，粗糙的表面同导电层和锌粉负极膜的粘接力更强，所涂的导电胶层为高纯石墨和不亲水粘接剂的混合物，可以有效阻止水对不锈钢集流体的腐蚀，防止电极膜与集流体箔材发生脱落。
在所述锌锰二次电池的化成过程中，先注入仅以水为溶剂的电解液进行初步化成，后加入醇类溶剂进行化成的方案，避免了醇在最初循环过程中过多参与副反应，导致更多的有害杂质生成，最初溶剂中仅有水参与反应，在常温下，优先构建水合固态电解质层，形成稳定的锌离子迁移壳层后，再引入醇，降低溶剂的凝固点，避免电解质盐在低温下析出，起到稳定和拓宽电解液工作温度的作用。
附图说明
图1、图2、图3为经过水热反应改性后的聚苯硫醚粉体的裂解气相色谱-质谱(PGC-MS)，用于证实反应产物中存在氯儿茶酚类结构分子。
图4为实施例2中聚苯硫醚固态隔膜的选择透过性试验，电渗析前后H型池的对比照片。
图5是本发明所述预制锌盐隔膜的结构示意图。
图6是实施例1中预制锌盐隔膜的图片。
图7是本发明中备注锌锰二次圆柱电池卷绕完成后的电池卷芯结构示意图。
图8是实施例1中的备注锌锰二次圆柱电池加注海水后的充放电的曲线图。
图9是实施例1中的备注锌锰二次圆柱电池加注海水后的充放电的循环图。
图10是实例3-7备注锌锰二次圆柱电池加注不同电解液后，容量的对比情况。
图11为实施例8焊点保护前备注锌锰二次电池的叠片芯包。
图12是实施例8焊点保护后备注锌锰二次电池的叠片芯包。
图13是实施例8铝塑膜包装的备注锌锰二次电池。
图14是实施例8中备注锌锰二次电池经过先水后醇的化成制度后稳定的循环曲线。
图15为实施例9中备注锌锰二次电池经过先水后醇的化成制度后在7℃的充放电曲线。
图16为实施例10中备注锌锰二次电池经过先水后醇的化成制度后在0℃的充放电曲线。
图17为实施例11中备注锌锰二次电池经过先水后醇的化成制度后在-10℃的充放电曲线。
图18为实施例12所述粉料处理系统的结构示意图。
图19为实施例12所述聚苯硫醚固态隔膜A的成膜流程图。
图20是实施例13所述聚苯硫醚固态隔膜A的表面SEM图。
图21是实施例13所述聚苯硫醚固态隔膜A的截面SEM图。
图22为实施例18所述负极膜的表面SEM图像。
图23为实施例18所述负极膜的截面的PTFE构成的空间缠结网络结构的SEM图像。
图中：1-上层支撑隔膜B，2-胶液C，3-聚苯硫醚固态隔膜A，4-胶液E，5-下层支撑膜F，6-预制锌盐隔膜H，7-正极，8-负极，9-卷芯。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。在本发明的一种实施方式中描述的元素和特征可以与一个或更多个其它实施方式中示出的元素和特征相结合。应当注意，为了清楚的目的，说明中省略了与本发明无关的、本领域普通技术人员已知的部件和处理的表示和描述。基于本发明中的实施例，本领域普通技术人员在没有付出创造 性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
适用于长寿命宽温区安时级锌锰二次电池固态隔膜的聚苯硫醚改性方法为：聚苯硫醚粉料、四氯对苯醌和去离子水三种原料混合后，进行水热反应，水热反应温度为180-240℃，恒温时间为1-4小时，反应气氛为空气、氧气、氮气或氩气。聚苯硫醚粉料、四氯对苯醌和去离子水三种原料的质量比为10:0.25-0.75:1-12。经过水热反应后，四氯对苯醌分子发生了氯离子去除，羟基增加的反应，生成了氯儿茶酚类结构的分子，包括2,5-二氯对苯二酚、2,3,5,6-四氯酚、3,4,5-三氯邻苯二酚、四氯氢醌、3,4,6-三氯邻苯二酚等一种或几种的混合物。
实施例1：聚苯硫醚改性
将聚苯硫醚粉料、四氯对苯醌和去离子水三种原料按照10:0.5:3的质量比配料混合，在210℃进行水热反应2小时，反应气氛为空气。水热反应结束后，将所得到的粉料经过裂解气相色谱-质谱(PGC-MS)检测后发现，四氯对苯醌分子发生了氯离子去除，羟基增加的反应，生成了氯儿茶酚类结构的分子，包括2,5-二氯对苯二酚、3,4,5-三氯邻苯二酚、四氯氢醌，分别如图1、图2、图3所示。
实施例2：聚苯硫醚改性
聚苯硫醚粉料、四氯对苯醌和去离子水三种原料按照10:0.5:6的质量比配料混合，在210℃进行水热反应2小时，反应气氛为空气。水热反应后，所得到的粉料经过裂解气相色谱-质谱(PGC-MS)检测后发现，四氯对苯醌分子发生了氯离子去除，羟基增加的反应，生成了氯儿茶酚类结构的分子，包括2,5-二氯对苯二酚、3,4,5-三氯邻苯二酚、四氯氢醌以及3,4,6-三氯邻苯二酚。
以改性后的聚苯硫醚制成的聚苯硫醚固态隔膜的选择透过性试验：采用H型池和电渗析法测试聚苯硫醚固态隔膜A的选择透过性，H型池的阳极池中加入70mL的pH＝4的无色透明稀硫酸，在阴极池中加入70mL深棕色透明水溶液的母液，母液的成分为1mol/L的ZnSO4,0.1mol/L的Na2SO4，0.1mol/L的Li2SO4，0.1mol/L的MnSO4，0.1mol/L的NiSO4，0.1mol/L的CoSO4，0.1mol/L的CuSO4，0.1mol/L的FeSO4，0.1mol/L的K2SO4，0.1mol/L的MgSO4。阳极和阴极均采用Pt金属电极，采用3.25V槽电压进行24小时持续电渗析试验。图4为电渗析前后H型池的对比照片，电渗析后，左侧阴极池稀硫酸无颜色变化，电极下方有大量沉积物，Pt电极表面有大量沉积和少量气泡。右侧阳极池依然为重金属的 深棕色。表1为ICP测定的母液在电渗析前后金属离子的浓度变化情况。证实只有锌离子透过了聚苯硫醚固态隔膜A，这是确保备注锌锰二次电池有较好性能的核心因素。
表1为母液在电渗析前后金属离子的浓度变化情况
本发明所述的预制锌盐隔膜，包括聚苯硫醚固态隔膜A和位于聚苯硫醚固态隔膜A两侧的上支撑隔膜B、下支撑隔膜F，在上支撑隔膜B、下支撑隔膜F与聚苯硫醚固态隔膜A之间分别填充有包括有机粘接剂和/或无机粘接剂与电解质锌盐的混合物。
如图5所示，位于上支撑隔膜B与聚苯硫醚固态隔膜A之间的胶液C与位于上支撑隔膜B、下支撑隔膜F与聚苯硫醚固态隔膜A之间的胶液E的成分含量可以相同，也可以不同。胶液C和胶液E中有机粘接剂、无机粘接剂和电解质盐和溶剂的比例为0-10：0-10：10-80：10-80，所述胶液C和胶液E的用量为5-30mg/cm2；经过烘干后形成固态的混合胶层，干胶单层负载为2-15mg/cm2，所述预制锌盐隔膜的厚度为70-200μm。其中有机粘接剂为聚乙烯醇(PVA)、聚丙烯酸酯(PAA)、聚四氟乙烯(PTFE)等聚合物粘接剂中的一种或多种的混合物；无机粘接剂为钠基膨润土、磷酸二氢锌、锂基蒙脱石粉等无机粉料中的一种或多种的混合物；电解质盐为三氟甲烷磺酸锌、硫酸锌、氯化锌、高氯酸锌等无机盐中的一种或多种的混合物；溶剂为去离子水、氮甲基吡咯烷酮(NMP)、酒 精、丙二醇等溶剂的一种或多种的混合物。
所述聚苯硫醚固态隔膜A的厚度为5-60μm。上层支撑隔膜B和下层支撑隔膜F均为多孔隔膜，其材质和厚度可以相同，也可以不同；选自厚度为3-30μm的聚乙烯隔膜(PE)、聚丙烯隔膜(PP)、纤维素膜、无纺布膜、PET膜等多孔隔膜。
所述预制锌盐隔膜的制备方法可以采用从胶液存放槽中蘸取胶液的方式，也可以采用涂覆的方式在隔膜上形成胶液，再将三层隔膜复合。下面的实施例以蘸取的方式为例来具体说明。
所述备注锌锰二次电池包括正极、负极和所述预制锌盐隔膜，将制锌盐隔膜H置于锰氧化物正极电极和锌负极电极之间，并进行极耳焊接，通过采用叠片机或卷绕机制备得到电池电芯，放入带有能够密封的注液口的电池壳内或铝塑膜袋内，封装备用和存储。在所述备注锌锰二次电池中，所述锰氧化物正极电极为采用半干法技术制造的二氧化锰干法电极，所述的锰氧化物为α-MnO2、β-MnO2、γ-MnO2、δ-MnO2、Mn2O3、Mn3O4、LiMn2O4等一种或几种锰氧化物的混合物。所述锌负极电极为采用半干法技术制造的锌粉干法电极、锌箔、镀锌铜箔等中的一种。
所述备注锌锰二次电池在存储过程中，不需要注液；需要使用电池时，在电池中注入纯水、海水或稀电解液，注入液体的量为1-20mL/Ah，封注液口后，得到能够充放电的锌锰二次电池。所述的稀电解液为浓度为0.01mol/L到1mol/L的硫酸锌、硫酸钠、硫酸镁、氯化钠、三氟甲烷磺酸锌等一种或几种的盐溶液，其溶剂为水、乙醇、甲醇、丙二醇、异丙醇、丙三醇中的一种或几种的混合物；稀电解液也可以直接为海水。
实施例3：预制锌盐隔膜及备注锌锰二次电池
将聚苯硫醚固态隔膜A通过导轨进入覆膜机，上层支撑隔膜B经过存放胶液C的胶槽沾取胶液C，并通过刮板刮去多余的胶液，与聚苯硫醚固态隔膜A在平台处进行复合，再经过辊压完成上层支撑隔膜B与固态隔膜A的复合。上层支撑隔膜B为亲水聚乙烯隔膜(PE)，胶液C由聚乙烯醇(PVA)、磷酸二氢锌、电解质盐三氟甲烷磺酸锌和水组成，四者质量比例为1:1:50:48。复合后的隔膜经过隧道炉烘干后进行裁切制得双层预制锌盐隔膜D，并收卷，隧道炉的温度为70℃。
将双层预制锌盐隔膜D的聚苯硫醚一侧经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，与下层支撑膜F在平台处进行复合，再经过辊压完成下层支撑隔膜F与双层预制锌盐隔膜D的复合。支撑隔膜F为亲水聚乙烯膜(PE)、胶液E由聚乙烯醇(PVA)、钠基膨润土、电解质盐三氟甲烷磺酸锌和水组成，四者质量比例为1:1:50:48。复合后的三层隔膜经过隧道炉烘干后制得三层预制锌盐隔膜H，并收卷。隧道炉的温度为70℃。本实施例制成的预制锌盐隔膜的外观如图6所示。
将β-MnO2干法电极与锌粉制成的干法电极分别作为正负极与预制锌盐隔膜H通过卷绕形成电芯，装入18650电池壳内制成备注锌锰二次圆柱电池。图7是备注锌锰二次圆柱电池卷绕完成后的电池卷芯的结构示意图。需要使用电池时，在电池中注入海水，注入海水的量为5mL/Ah，封注液口后，锌锰二次电池即可进行充放电。图8为本实施例中的备注锌锰二次圆柱电池加注海水后，充放电的曲线图，其充放电曲线与常规的锌锰二次电池的曲线一致。图9是本实施例中的备注锌锰二次圆柱电池加注海水后，充放电的循环图。电池循环稳定，150圈无明显衰减。
进一步地，为了确保极片裸露处不会在充放电过程中发生析氢和析氧的副反应，本实施例在β-MnO2干法电极与锌粉制成的干法电极的集流体裸露处贴绝缘绝水胶带进行保护，不锈钢集流体和极耳通过电阻焊焊接在一起。所述备注锌锰二次电池外包装采用PP材质，外部有加持机构，将极间距减小为65μm。
实施例4：预制锌盐隔膜及备注锌锰二次电池
将聚苯硫醚固态隔膜A通过导轨进入覆膜机，上层支撑隔膜B经过存放胶液C的胶槽沾取胶液C，并通过刮板刮去多余的胶液，与聚苯硫醚固态隔膜A在平台处进行复合，再经过辊压完成上层支撑隔膜B与固态隔膜A的复合。上层支撑隔膜B为亲水聚丙烯隔膜(PP)，胶液C由聚丙烯酸酯(PAA)、磷酸二氢锌、电解质盐三氟甲烷磺酸锌和水组成，四者质量比例为1:2:45:52。复合后的隔膜经过隧道炉烘干后进行裁切制得双层预制锌盐隔膜D，并收卷，隧道炉的温度为80℃。
将双层预制锌盐隔膜D的聚苯硫醚一侧经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，与下层支撑膜F在平台处进行复合，再经过辊压完 成下层支撑隔膜F与双层预制锌盐隔膜D的复合。支撑隔膜F为亲水聚乙烯膜(PE)、胶液E由聚丙烯酸酯(PAA)、锂基蒙脱石粉、电解质盐三氟甲烷磺酸锌和水组成，四者质量比例为1:2:45:52。复合后的三层隔膜经过隧道炉烘干后制得三层预制锌盐隔膜H，并收卷。隧道炉的温度为80℃。
将γ-MnO2干法电极与锌箔分别作为正负极与预制锌盐隔膜H通过叠片工艺形成电芯，装入铝塑膜内制成备注锌锰二次电池。需要使用电池时，在电池中注入0.5mol/L的ZnSO4溶液，注入ZnSO4溶液的量为10mL/Ah，封注液口后，即可进行充放电。
实施例5：预制锌盐隔膜及备注锌锰二次电池
将聚苯硫醚固态隔膜A通过导轨进入覆膜机，上层支撑隔膜B经过存放胶液C的胶槽沾取胶液C，并通过刮板刮去多余的胶液，与聚苯硫醚固态隔膜A在平台处进行复合，再经过辊压完成上层支撑隔膜B与固态隔膜A的复合。上层支撑隔膜B为亲水聚丙烯隔膜(PP)，胶液C由聚四氟乙烯(PTFE)、磷酸二氢锌、电解质盐硫酸锌和水组成，四者质量比例为5:7:38:50。复合后的隔膜经过隧道炉烘干后进行裁切制得双层预制锌盐隔膜D，并收卷，隧道炉的温度为100℃。
将双层预制锌盐隔膜D的聚苯硫醚一侧经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，与下层支撑膜F在平台处进行复合，再经过辊压完成下层支撑隔膜F与双层预制锌盐隔膜D的复合。支撑隔膜F为亲水聚乙烯膜(PE)、胶液E由聚四氟乙烯(PTFE)、锂基蒙脱石粉、电解质盐硫酸锌和水组成，四者质量比例为5:7:38:50。复合后的三层隔膜经过隧道炉烘干后制得三层预制锌盐隔膜H，并收卷。隧道炉的温度为100℃。
将LiMn2O4干法电极与锌粉制成的干法电极分别作为正负极与预制锌盐隔膜H通过叠片工艺形成电芯，装入铝塑膜内制成备注锌锰二次电池。需要使用电池时，在电池中注入水，注入水的量为8mL/Ah，封注液口后，即可进行充放电。
实施例6：预制锌盐隔膜及备注锌锰二次电池
将聚苯硫醚固态隔膜A通过导轨进入覆膜机，上层支撑隔膜B经过存放胶液C的胶槽沾取胶液C，并通过刮板刮去多余的胶液，与聚苯硫醚固态隔膜A在平台处进行复合，再经过辊压完成上层支撑隔膜B与固态隔膜A的复合。上 层支撑隔膜B为亲水聚丙烯隔膜(PP)，胶液C由聚四氟乙烯(PTFE)、磷酸二氢锌、电解质盐硫酸锌和水组成，四者质量比例为5:7:38:50。复合后的隔膜经过隧道炉烘干后进行裁切制得双层预制锌盐隔膜D，并收卷，隧道炉的温度为100℃。
将双层预制锌盐隔膜D的聚苯硫醚一侧经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，与下层支撑膜F在平台处进行复合，再经过辊压完成下层支撑隔膜F与双层预制锌盐隔膜D的复合。支撑隔膜F为亲水聚乙烯膜(PE)、胶液E由聚四氟乙烯(PTFE)、锂基蒙脱石粉、电解质盐硫酸锌和水组成，四者质量比例为5:7:38:50。复合后的三层隔膜经过隧道炉烘干后制得三层预制锌盐隔膜H，并收卷。隧道炉的温度为100℃。
将LiMn2O4干法电极与锌粉制成的干法电极分别作为正负极与预制锌盐隔膜H通过叠片工艺形成电芯，装入铝塑膜内制成备注锌锰二次电池。需要使用电池时，在电池中注入1mol/L的MgSO4和NaCl混合溶液，注入混合溶液的量为7mL/Ah，封注液口后，即可进行充放电。
实施例7：预制锌盐隔膜及备注锌锰二次电池
将聚苯硫醚固态隔膜A通过导轨进入覆膜机，上层支撑隔膜B经过存放胶液C的胶槽沾取胶液C，并通过刮板刮去多余的胶液，与聚苯硫醚固态隔膜A在平台处进行复合，再经过辊压完成上层支撑隔膜B与固态隔膜A的复合。上层支撑隔膜B为纤维素隔膜，胶液C由聚四氟乙烯(PTFE)、磷酸二氢锌、电解质盐硫酸锌和水组成，四者质量比例为4:2:52:40。复合后的隔膜经过隧道炉烘干后进行裁切制得双层预制锌盐隔膜D，并收卷，隧道炉的温度为85℃。
将双层预制锌盐隔膜D的聚苯硫醚一侧经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，与下层支撑膜F在平台处进行复合，再经过辊压完成下层支撑隔膜F与双层预制锌盐隔膜D的复合。支撑隔膜F为纤维素隔膜、胶液E由聚四氟乙烯(PTFE)、锂基蒙脱石粉、电解质盐硫酸锌和水组成，四者质量比例为4:2:52:40。复合后的三层隔膜经过隧道炉烘干后制得三层预制锌盐隔膜H，并收卷。隧道炉的温度为85℃。
将LiMn2O4干法电极与锌粉制成的干法电极分别作为正负极与预制锌盐隔膜H通过叠片工艺形成电芯，装入铝塑膜内制成备注锌锰二次电池。需要使用电池时，在电池中注入1mol/L的Na2SO4和KCl混合溶液，注入混合溶液的量 为8mL/Ah，封注液口后，即可进行充放电。
图10是实例3-7备注锌锰二次电池加注不同电解液后，容量的对比情况。可以明显看出加入不同于锌离子的其他阳离子，构成了双离子和多离子体系所表达出的容量更大，体现出的电池的能量密度更高。
实施例8
为了避免锌锰二次电池在充放电过程中的副反应的发生，本实施例中的锌锰二次电池以γ-MnO2半干法正极，锌粉半干法负极为电极，以实施例1经过水热改性后的聚苯硫醚粉体制成的聚苯硫醚固态隔膜来制作预制锌盐隔膜，将电极、预制锌盐隔膜材料完成叠片后，不锈钢集流体与镍极耳采用电阻焊接。焊接完成后，焊接点采用环氧树脂进行保护，以实现阻水绝缘效果，图11和图12分别是焊点保护前后的锌锰二次电池的叠片芯包，并以铝塑膜为外包装材料进行封装，如图13所示。
进一步地，本实施例还涉及到上述制得的锌锰二次电池的化成方法，具体为：电池先注入1mol/L的硫酸钠水溶液，注液量为7mL/Ah。以10mA/g的小电流化成进行一次放电，并以该小电流充放电3圈后，在电池放电状态下，注入甲醇，水溶液电解液和醇的体积比为5:0.7，再进行真空封装。图14为本实施例制备的锌锰二次电池经过先水后醇的化成制度后在7℃的充放电曲线。
实施例9
为了避免锌锰二次电池在充放电过程中的副反应的发生，本实施例中的锌锰二次电池以γ-MnO2半干法正极、锌粉半干法负极为和电极，将实施例2水热改性后的聚苯硫醚粉末制成的聚苯硫醚固态隔膜来制作预制锌盐隔膜，将电极与预制锌盐隔膜材料完成叠片后，正极的不锈钢集流体与镍极耳、负极的铜集流体与铜极耳之间采用电阻焊焊接，焊接点采用不饱和聚酯进行保护。
进一步地，本实施例还涉及到上述制得的锌锰二次电池的化成方法，具体为：电池先注入1mol/L的氯化钠水溶液，注液量为8mL/Ah。以20mA/g小电流化成进行一次放电，小电流充放电10圈后，在电池放电状态下，注入异丙醇，水溶液电解液和醇的体积比为5:2，再进行真空封装。图15为本实施例制备的锌锰二次电池经过先水后醇的化成制度后稳定的循环曲线。
实施例10
为了避免锌锰二次电池在充放电过程中的副反应的发生，本实施例中的锌锰二次电池以ε-MnO2半干法正极、锌粉半干法负极为电极，以经过水热改性后的聚苯硫醚粉末制成的聚苯硫醚固态隔膜来制作预制锌盐隔膜。将电极和隔膜材料完成叠片后，不锈钢集流体与钛极耳焊接，采用电阻焊接，焊接点采用环氧树脂进行保护。
进一步地，本实施例还涉及到上述制得的锌锰二次电池的化成方法，具体为：电池先注入1mol/L的硫酸锌水溶液，注液量为10mL/Ah。以20mA/g小电流化成进行一次放电，小电流充放电10圈后，在电池放电状态下，注入乙二醇，水溶液电解液和醇的体积比为5:3，再进行真空封装。图16为本实施例制备的备注锌锰二次电池经过先水后醇的化成制度后在0℃的充放电曲线。
实施例11
为了避免锌锰二次电池在充放电过程中的副反应的发生，本实施例中的备注锌锰二次电池以β-MnO2半干法正极、锌粉半干法负极和经过水热改性后的聚苯硫醚粉末制成的聚苯硫醚固态隔膜为来制作预制锌盐隔膜，完成叠片后，正极的不锈钢集流体与镍极耳，负极的铜集流体与铜极耳焊接，采用电阻焊接，焊接点采用呋喃树脂进行保护。
进一步地，本实施例还涉及到上述制得的锌锰二次电池的化成方法，具体为：电池先注入1mol/L的三氟甲磺酸锌水溶液，注液量为8mL/Ah。以20mA/g小电流化成进行一次放电，小电流充放电5圈后，在电池放电状态下，注入异丙醇，水溶液电解液和醇的体积比为5:5，再进行真空封装。图17为本实施例制备的锌锰二次电池经过先水后醇的化成制度后在-10℃的充放电曲线。
实施例12：聚苯硫醚固态隔膜的制造设备及方法
本实施例公开的是聚苯硫醚固态隔膜的制造设备，包括粉料处理系统、高速剪切机、螺杆挤出机、卧式冷辊压机、卧式热辊压机。
所述粉料处理系统包括依次连通的空压机、储气罐、冷干机、干燥吸附塔、净化柱，以及空气预热系统、粉料加热系统、超音速剪切混料机、气固分离塔，图18为本实施例所述粉料处理系统的结构示意图。超音速剪切混料机具有半封闭型腔，所述净化柱的出气口与超音速剪切混料机的半封闭型腔的进气口连通，且空气预热系统设置在净化柱与超音速剪切混料机之间的空气管路上。所述粉料 加热系统设置在超音速剪切混料机半封闭型腔的下料口处。所述超音速剪切混料机半封闭型腔的出料口通过管道与气固分离塔连通，气固分离塔的上部设有出气口、底部设有出料口、中部设有气锤进气孔。所述干燥吸附塔的数量为多个，多个干燥吸附塔并联设置，分别与冷干机出气口、净化柱进气口连通。所述气锤的气体来源为净化柱后的干燥压缩空气旁路，通过间歇式释放压缩空气实现气锤功能。
经粉料处理系统处理的粉料的制膜流过程是由图19所示高速剪切机、螺杆挤出机、卧式冷辊压机、卧式热辊压机完成。经粉料处理系统处理的粉料被送入高速剪切机，经剪切后进入螺杆挤出机，所述卧式冷辊压机、卧式热辊压机依次设置在螺杆挤出机的下游，且卧式冷辊压机与卧式热辊压机之间设置加热输送导轨。
实施例13：聚苯硫醚固态隔膜的制备方法
本实施例公开了一种利用所述聚苯硫醚固态隔膜的制造设备制备聚苯硫醚固态隔膜的方法，具体步骤如下：
将3质量份的LiCl溶解在12质量份去离子水中制成LiCl溶液，0.5质量份的四氯对苯醌与10质量份的交联态高结晶聚苯硫醚粉料(结晶度>70％)混合制成混合粉体C，将LiCl溶液与混合粉体C混合成浆料D，浆料D装入密闭反应釜中，进行水热反应，水热反应气氛为空气，温度为210℃，反应时间为2小时，水热反应装填率为30％，反应结束后粉料清洗呈中性烘干，制成粉料E。
将6wt％聚四氟乙烯粉体和94wt％粉料E在混料机中混合均匀至粉料F，混合过程在聚四氟乙烯呈玻璃态的温度条件下进行。干燥的大气环境空气G(RH＝5％)经过15KW空压机压缩，冷干，干燥吸附，净化，干燥吸附过程为，采用两个内含分子筛的干燥吸附塔，分子筛总重400kg，两个塔交替工作和再生，交替时间为6分钟。干燥净化后的气体45℃预热后，通过喷管，进入半封闭型腔，被加速到超音速，形成极干燥空气的超音速射流H，露点-40℃。粉料F经过100℃预热加入到半封闭型腔中，被极干燥空气的超音速射流H摩擦剪切，粉料F中的聚四氟乙烯的分子链延展打开，同F中的粉体形成物理粘连，且不发生化学反应，获得粉料I；粉料I随气流被吹入固气分离塔中，分离塔内部有除尘滤芯，用以分离固体分料和气体，气体直接排出，滤芯上的粘附粉料被气锤吹 震到下方的收料桶里，气锤的气体来源为净化后的干燥压缩空气旁路，通过间歇式释放压缩空气实现气锤功能。
粉料I加入到高速剪切机中，进行二次纤维化，出料后进入到螺杆挤出机中，挤出呈10条连续的粗条J，粗条J的直径为8mm，并进入到辊面温度为20℃的卧式冷辊压机进行一次减薄到0.8mm，减薄后进入到130℃的加热输送导轨中，边加热边上料进入到辊面温度为130℃卧式热辊压机中，进行二次减薄至30μm，并切去两边缘，制成成品的固态隔膜L，并收卷，切边料K回收后加入到高速剪切机中进行回用。图20为固态隔膜的表面SEM图，图21是固态隔膜的截面SEM图，固态隔膜由纤维状PTFE形成的缠结网络结构和塑性变形的PPS晶体颗粒组成的致密膜，孔隙率极低，该图中的孔隙率积分计算是3％。
实施例14：聚苯硫醚固态隔膜的制备方法
将1质量份的NaCl溶解在9质量份去离子水中制成NaCl溶液，0.25质量份的四氯对苯醌与10质量份的交联态高结晶聚苯硫醚粉料(结晶度>60％)混合制成混合粉体C，将NaCl溶液与混合粉体C混合成浆料D，浆料D装入密闭反应釜中，进行水热反应，水热反应气氛为空气，温度为200℃，反应时间为3小时，水热反应装填率为40％，反应结束后粉料清洗呈中性烘干，制成粉料E。
将5wt％聚四氟乙烯粉体和95wt％粉料E在混料机中混合均匀至粉料F，混合过程在聚四氟乙烯呈玻璃态的温度条件下进行。干燥的大气环境空气G(RH＝8％)经过30KW空压机压缩，冷干，干燥吸附，净化，干燥吸附过程为，采用两个内含分子筛的干燥吸附塔，分子筛总重500kg，两个塔交替工作和再生，交替时间为8分钟。干燥净化后的气体50℃预热后，通过喷管，进入半封闭型腔，被加速到超音速，形成极干燥空气的超音速射流H，露点-45℃。粉料F经过120℃预热加入到半封闭型腔中，被极干燥空气的超音速射流H摩擦剪切，粉料F中的聚四氟乙烯的分子链延展打开，同F中的粉体形成物理粘连，且不发生化学反应，获得粉料I；粉料I随气流被吹入固气分离塔中，分离塔内部有除尘滤芯，用以分离固体分料和气体，气体直接排出，滤芯上的粘附粉料被气锤吹震到下方的收料桶里，气锤的气体来源为净化后的干燥压缩空气旁路，通过间歇式释放压缩空气实现气锤功能。
粉料I加入到高速剪切机中，进行二次纤维化，出料后进入到螺杆挤出机中， 挤出呈连续厚饼J，连续厚饼J的直径为10mm，并进入到辊面温度为10℃的卧式冷辊压机进行一次减薄到1mm，减薄后进入到130℃的加热输送导轨中，边加热边上料进入到辊面温度为120℃卧式热辊压机中，进行二次减薄至35μm，并切去两边缘，制成成品的固态隔膜L，并收卷，切边料K回收后加入到高速剪切机中进行回用。
实施例15：聚苯硫醚固态隔膜的制备方法
将2质量份的ZnCl2溶解在10质量份去离子水中制成ZnCl2溶液，0.3质量份的四氯对苯醌与10质量份的交联态高结晶聚苯硫醚粉料(结晶度>60％)混合制成混合粉体C，将ZnCl2溶液与混合粉体C混合成浆料D，浆料D装入密闭反应釜中，进行水热反应，水热反应气氛为氩气，温度为220℃，反应时间为1.5小时，水热反应装填率为50％，反应结束后粉料清洗呈中性烘干，制成粉料E。
将4wt％聚四氟乙烯粉体和96wt％粉料E在混料机中混合均匀至粉料F，混合过程在聚四氟乙烯呈玻璃态的温度条件下进行。干燥的大气环境空气G(RH＝6％)经过30KW空压机压缩，冷干，干燥吸附，净化，干燥吸附过程为，采用两个内含分子筛的干燥吸附塔，分子筛总重1000kg，两个塔交替工作和再生，交替时间为7分钟。干燥净化后的气体47℃预热后，通过喷管，进入半封闭型腔，被加速到超音速，形成极干燥空气的超音速射流H，露点-42℃。粉料F经过125℃预热加入到半封闭型腔中，被极干燥空气的超音速射流H摩擦剪切，粉料F中的聚四氟乙烯的分子链延展打开，同F中的粉体形成物理粘连，且不发生化学反应，获得粉料I；粉料I随气流被吹入固气分离塔中，分离塔内部有除尘滤芯，用以分离固体分料和气体，气体直接排出，滤芯上的粘附粉料被气锤吹震到下方的收料桶里，气锤的气体来源为净化后的干燥压缩空气旁路，通过间歇式释放压缩空气实现气锤功能。
粉料I加入到高速剪切机中，进行二次纤维化，出料后进入到螺杆挤出机中，挤出呈连续厚饼J，连续厚饼J的直径为7mm，并进入到辊面温度为25℃的卧式冷辊压机进行一次减薄到0.8mm，减薄后进入到130℃的加热输送导轨中，边加热边上料进入到辊面温度为130℃卧式热辊压机中，进行二次减薄至40μm，并切去两边缘，制成成品的固态隔膜L，并收卷，切边料K回收后加入到高速剪切机中进行回用。
实施例16：聚苯硫醚固态隔膜的制备方法
将3.5质量份的MgCl2溶解在9质量份去离子水中制成MgCl2溶液，0.45质量份的四氯对苯醌与11质量份的交联态高结晶聚苯硫醚粉料(结晶度>60％)混合制成混合粉体C，将MgCl2溶液与混合粉体C混合成浆料D，浆料D装入密闭反应釜中，进行水热反应，水热反应气氛为空气，温度为215℃，反应时间为3小时，水热反应装填率为30％，反应结束后粉料清洗呈中性烘干，制成粉料E。
将4wt％聚四氟乙烯粉体和96wt％粉料E在混料机中混合均匀至粉料F，混合过程在聚四氟乙烯呈玻璃态的温度条件下进行。干燥的大气环境空气G(RH＝6％)经过30KW空压机压缩，冷干，干燥吸附，净化，干燥吸附过程为，采用两个内含分子筛的干燥吸附塔，分子筛总重600kg，两个塔交替工作和再生，交替时间为8分钟。干燥净化后的气体45℃预热后，通过喷管，进入半封闭型腔，被加速到超音速，形成极干燥空气的超音速射流H，露点-40℃。粉料F经过130℃预热加入到半封闭型腔中，被极干燥空气的超音速射流H摩擦剪切，粉料F中的聚四氟乙烯的分子链延展打开，同F中的粉体形成物理粘连，且不发生化学反应，获得粉料I；粉料I随气流被吹入固气分离塔中，分离塔内部有除尘滤芯，用以分离固体分料和气体，气体直接排出，滤芯上的粘附粉料被气锤吹震到下方的收料桶里，气锤的气体来源为净化后的干燥压缩空气旁路，通过间歇式释放压缩空气实现气锤功能。
粉料I加入到高速剪切机中，进行二次纤维化，出料后进入到螺杆挤出机中，挤出呈连续厚饼J，连续厚饼J的直径为9mm，并进入到辊面温度为15℃的卧式冷辊压机进行一次减薄到0.9mm，减薄后进入到130℃的加热输送导轨中，边加热边上料进入到辊面温度为130℃卧式热辊压机中，进行二次减薄至40μm，并切去两边缘，制成成品的固态隔膜L，并收卷，切边料K回收后加入到高速剪切机中进行回用。
实施例17：锰氧化物正极电极的制造方法，
首先将二氧化锰与聚四氟乙烯混合后，在聚四氟乙烯的玻璃化转变温度以下，采用干燥的超音速射流气体喷射使聚四氟乙烯的分子链打开与正极材料粉末物理粘连，再纤维化的粉料中喷洒醇溶液，经过密炼、剪切造粒后热辊压为正极膜， 再经多次冷辊压将多层正极膜复合成厚度为100-150μm的复合正极自支撑膜，最后将复合正极自支撑膜与表面涂过胶的喷砂不锈钢箔通过热辊压机复合在一起。
实施例18：锌负极电极的制造方法，
将锌粉、ECP、高纯石墨、蒙脱石粉、氯化铟按照74wt％：7wt％：5wt％：5wt％：1wt％，在混料机中混合均匀至粉料A；将8wt％聚四氟乙烯粉体和92wt％粉料A在0℃的混料机中混合均匀至粉料B；料B在行星球磨仪中，加入乙醇和去离子水按照1:1的体积比配制而成的混合溶剂，在润湿的状态下通过球磨珠的高速转动，不断摩擦使得PTFE拉丝呈网状结构，氯化铟与锌粉发生还原反应，待上述过程结束后，过滤获得胶团C；胶团C经密炼后形成均匀胶团，该胶团经过剪切造粒后制成大小均一的毫米级颗粒料E，固含量在50％；颗粒E经卧式热辊压机辊压一次达到150μm负极膜F，热辊压温度为80℃。负极膜F在卧式热辊下方经过完成切边，达到膜材宽度要求，切边料可再次剪碎，并投入到颗粒料E中，完成边料回用。切边后的负极膜F贴覆到多孔离型纸的托带上，完成收卷。收卷后，整卷进行干燥，脱去部分溶剂，半干状态的负极膜F的固含量在65％。负极膜F的表面和截面的结构如图22和图23所示，PTFE形成的缠结网络结构可以使得电极的结构更加稳定。采用热压复合工艺，将揭掉离型纸后的半干燥负极膜F热复合在涂胶不锈钢箔的两面制成电极。
实施例19：锌负极电极的制造方法
将锌粉、SP、高纯石墨、伊利石粉、氯化铜按照50wt％：15wt％：15wt％：10wt％：2wt％，在混料机中混合均匀至粉料A；将8wt％聚四氟乙烯粉体和92wt％粉料A在5℃的混料机中混合均匀至粉料B；料B在行星球磨仪中，加入一定的醇类溶剂，在润湿的状态下通过球磨珠的高速转动，不断摩擦使得其拉丝呈网状结构，粉料B中的聚四氟乙烯的分子链延展打开，同A中的粉体形成物理粘连，氯化铜与锌粉发生还原反应，待上述过程结束后，过滤获得胶团C；胶团C经密炼后形成均匀胶团，该胶团经过剪切造粒后制成大小均一的毫米级颗粒料E，固含量在75％；颗粒E经卧式热辊压机辊压一次达到120μm负极膜F，热辊压温度为90℃。负极膜F在卧式热辊下方经过完成切边，达到膜材宽度要求，切边料可再次剪碎，并投入到颗粒料E中，完成边料回用。切边后的 负极膜F贴覆到多孔离型纸的托带上，完成收卷。收卷后，整卷进行干燥，脱去部分溶剂，半干状态的负极膜F的固含量在60％。采用热压复合工艺，将揭掉离型纸后的半干燥负极膜F热复合在涂胶不锈钢箔的两面制成电极。
实施例20：锌负极电极的制造方法
将锌粉、ECP、人造石墨、高岭土、硫酸铟按照60wt％：10wt％：8wt％：10wt％：4wt％，在混料机中混合均匀至粉料A；将8wt％聚四氟乙烯粉体和92wt％粉料A在5℃的混料机中混合均匀至粉料B；粉料B在行星球磨仪中，加入一定的醇类溶剂，在润湿的状态下通过球磨珠的高速转动，不断摩擦使得其拉丝呈网状结构，粉料B中的聚四氟乙烯的分子链延展打开，同A中的粉体形成物理粘连，硫酸铟与锌粉发生还原反应，待上述过程结束后，过滤获得胶团C；胶团C经密炼后形成均匀胶团，该胶团经过剪切造粒后制成大小均一的毫米级颗粒料E，固含量在75％；颗粒E经卧式热辊压机辊压一次达到120μm负极膜F，热辊压温度为90℃。负极膜F在卧式热辊下方经过完成切边，达到膜材宽度要求，切边料可再次剪碎，并投入到颗粒料E中，完成边料回用。切边后的负极膜F贴覆到多孔离型纸的托带上，完成收卷。收卷后，整卷进行干燥，脱去部分溶剂，半干状态的负极膜F的固含量在60％。采用热压复合工艺，将揭掉离型纸后的半干燥负极膜F热复合在涂胶不锈钢箔的两面制成电极。
实施例21：锌负极电极的制造方法
将锌粉、SP、人造石墨、埃洛石粉、硫酸铜按照67wt％：5wt％：5wt％：10wt％：5wt％，在混料机中混合均匀至粉料A；将8wt％聚四氟乙烯粉体和92wt％粉料A在0℃的混料机中混合均匀至粉料B；料B在行星球磨仪中，加入一定的醇类溶剂，在润湿的状态下通过球磨珠的高速转动，不断摩擦使得其拉丝呈网状结构，粉料B中的聚四氟乙烯的分子链延展打开，同A中的粉体形成物理粘连，硫酸铜与锌粉发生还原反应，待上述过程结束后，过滤获得胶团C；胶团C经密炼后形成均匀胶团，该胶团经过剪切造粒后制成大小均一的毫米级颗粒料E，固含量在70％；颗粒E经卧式热辊压机辊压一次达到100μm负极膜F，热辊压温度为95℃。负极膜F在卧式热辊下方经过完成切边，达到膜材宽度要求，切边料可再次剪碎，并投入到颗粒料E中，完成边料回用。切边后的负极膜F贴覆到多孔离型纸的托带上，完成收卷。收卷后，整卷进行干燥，脱去 部分溶剂，半干状态的负极膜F的固含量在55％。采用热压复合工艺，将揭掉离型纸后的半干燥负极膜F热复合在涂胶不锈钢箔的两面制成电极。

Claims (41)

  1. 一种聚苯硫醚改性方法，其特征在于：将聚苯硫醚粉料、四氯对苯醌和去离子水按照10:0.25-0.75:1-12的质量比混合后，于180-240℃进行水热反应，在水热反应过程中四氯对苯醌分子发生了氯离子去除，羟基增加的反应，生成了氯儿茶酚类结构的分子。
  2. 根据权利要求1所述的聚苯硫醚改性方法，其特征在于，所述水热反应温的恒温时间为1-4小时，反应气氛为空气、氧气、氮气或氩气。
  3. 权利要求1-2任一项所述的聚苯硫醚改性方法制成的改性聚苯硫醚，其特征在于，在聚苯硫醚固态隔膜中负载有氯儿茶酚类结构的分子；所述的氯儿茶酚类结构分子为2,5-二氯对苯二酚、2,3,5,6-四氯酚、3,4,5-三氯邻苯二酚、四氯氢醌、3,4,6-三氯邻苯二酚等一种或几种的混合物。
  4. 由权利有要求3所述的改性聚苯硫醚制成的聚苯硫醚固态隔膜。
  5. 由权利有要求4所述的聚苯硫醚固态隔膜，其特征在于，所述聚苯硫醚固态隔膜具有锌离子选择透过性。
  6. 预制锌盐隔膜的制造方法，其特征在于，包括以下步骤：
    (1)将聚苯硫醚固态隔膜A、上层支撑隔膜B中的一个在沾取或者涂覆胶液C后将两者贴合，使胶液C位于聚苯硫醚固态隔膜A与上层支撑隔膜B之间，再经过辊压使上层支撑隔膜B与固态隔膜A的复合；复合后的上层支撑隔膜B与固态隔膜A经过烘干后制得双层预制锌盐隔膜D；
    (2)将双层预制锌盐隔膜D的聚苯硫醚固态隔膜A裸露表面、下层支撑膜F中的一个在沾取或者涂覆胶液E后将两者贴合，使胶液E位于，经过存放胶液E的胶槽沾取胶液E，并通过刮板刮去多余的胶液，或者将胶液E聚苯硫醚固态隔膜A与下层支撑膜F之间，再经过辊压使下层支撑隔膜F与双层预制锌盐隔膜D的复合，复合后的三层隔膜经烘干后制得预制锌盐隔膜H；
    所述上层支撑隔膜B和下层支撑隔膜F均为多孔隔膜，所述胶液C和胶液E为有机粘接剂和/或无机粘接剂与电解质锌盐、溶剂的混合物。
  7. 根据权利要求6所述的预制锌盐隔膜的制造方法，其特征在于：所述有机粘接剂、无机粘接剂和电解质盐和溶剂的质量比为0-10：0-10：10-80：10-80。
  8. 根据权利要求6所述的预制锌盐隔膜的制造方法，其特征在于：所述有机粘接剂为聚乙烯醇(PVA)、聚丙烯酸酯(PAA)、聚四氟乙烯(PTFE)中的一 种或多种的混合物；无机粘接剂为钠基膨润土、磷酸二氢锌、锂基蒙脱石粉中的一种或多种的混合物；电解质锌盐为三氟甲烷磺酸锌、硫酸锌、氯化锌、高氯酸锌中的一种或几种的混合物；溶剂为去离子水、氮甲基吡咯烷酮(NMP)、酒精、丙二醇的一种或几种的混合物。
  9. 根据权利要求6所述的预制锌盐隔膜的制造方法，其特征在于：所述聚苯硫醚固态隔膜A的厚度为5-60μm，所述多孔隔膜为聚乙烯隔膜(PE)、聚丙烯隔膜(PP)、纤维素膜、无纺布膜、PET膜中的一种，其厚度为3-30μm。
  10. 根据权利要求6所述的预制锌盐隔膜的制造方法，其特征在于：所述胶液C、胶液E的用量为5-30mg/cm2；两次的烘干温度均为50-100℃；烘干后，干胶单层负载为2-15mg/cm2，所述预制锌盐隔膜H的厚度为70-200μm。
  11. 根据权利要求6所述的预制锌盐隔膜的制造方法，其特征在于：所述聚苯硫醚固态隔膜A是由权利要求3或4中所述的改性聚苯硫醚制成的。
  12. 根据权利要求10所述的预制锌盐隔膜的制造方法，其特征在于：所述聚苯硫醚固态隔膜A的制造设备，包括粉料处理系统、高速剪切机、螺杆挤出机、卧式冷辊压机、卧式热辊压机；
    所述粉料处理系统包括依次连通的空压机、储气罐、冷干机、干燥吸附塔、净化柱，以及空气预热系统、粉料加热系统、超音速剪切混料机、气固分离塔；超音速剪切混料机具有半封闭型腔，所述净化柱的出气口与超音速剪切混料机的半封闭型腔的进气口连通，且空气预热系统设置在净化柱与超音速剪切混料机之间的空气管路上；所述粉料加热系统设置在超音速剪切混料机半封闭型腔的下料口处；所述超音速剪切混料机半封闭型腔的出料口通过管道与气固分离塔连通，气固分离塔的上部设有出气口、底部设有出料口、中部设有气锤进气孔；
    经粉料处理系统处理的粉料被送入高速剪切机，经剪切后进入螺杆挤出机，所述卧式冷辊压机、卧式热辊压机依次设置在螺杆挤出机的下游，且卧式冷辊压机与卧式热辊压机之间设置加热输送导轨。
  13. 根据权利要求12所述的预制锌盐隔膜的制造方法，其特征在于：所述干燥吸附塔的数量为多个，多个干燥吸附塔并联设置，分别与冷干机出气口、净化柱进气口连通；所述气锤的气体来源为净化柱后的干燥压缩空气旁路，通 过间歇式释放压缩空气实现气锤功能。
  14. 根据权利要求12或13所述的预制锌盐隔膜的制造方法，其特征在于：所述聚苯硫醚固态隔膜A的制造方法，包括以下步骤：
    (1)制粉：
    将金属氯化物A溶解在去离子水中制成溶液B，四氯对苯醌与聚苯硫醚粉料混合制成混合粉体C，将溶液B与混合粉体C混合成浆料D，浆料D装入密闭反应釜中，进行水热反应，反应结束后粉料清洗呈中性烘干，制成粉料E；
    (2)纤维化：
    将聚四氟乙烯粉体和粉料E在混料机中混合均匀至粉料F，混合过程在聚四氟乙烯呈玻璃态的温度条件下进行；
    干燥的空气G经过空压机压缩、冷干、干燥吸附、净化、预热后，通过喷管，进入半封闭型腔，被加速到超音速，形成极干燥空气的超音速射流H；
    粉料F经过预热加入到半封闭型腔中，被极干燥空气的超音速射流H摩擦剪切，粉料F中的聚四氟乙烯的分子链延展打开，同F中的粉体形成物理粘连，且不发生化学反应，获得粉料I；
    粉料I随气流被吹入固气分离塔中，分离塔内部有除尘滤芯，用以分离固体粉料和气体，气体直接排出，滤芯上粘附的粉料被气锤吹震到下方的收料桶里；
    (3)制膜：
    粉料I加入到高速剪切机中，进行二次纤维化，出料后进入到螺杆挤出机中，挤出呈多条连续的粗条或连续厚饼J，并进入到卧式冷辊压机进行一次减薄，减薄后进入到加热输送导轨中，边加热边上料进入到卧式热辊压机中，进行二次减薄，并切去两边缘，制成成品的固态隔膜L，并收卷。
  15. 根据权利要求14所述的预制锌盐隔膜的制造方法，其特征在于：所述制粉工艺中的金属氯化物A为氯化锂、氯化钠、氯化锌、氯化镁、氯化铝中的一种或几种的混合物；所述的聚苯硫醚粉料为交联态高结晶聚苯硫醚粉料，结晶度>60％，粉料的D50为3-25μm；所述的金属氯化物，去离子水，四氯对苯醌，聚苯硫醚的质量比为0-3:3-30:0.1-0.75:5-15；所述的水热反应釜内的气氛为空气或氩气，所述水热反应温度为150-250℃，所述水热反应时间为1-4小时； 水热反应的体积填充率为20％-70％。
  16. 根据权利要求14所述的预制锌盐隔膜的制造方法，其特征在于：所述纤维化过程中，干燥空气G，其室温25℃下相对湿度(RH)<10％；所述的空压机的功率大于等于15kW，连续化生产优选30kW以上；所述的极干燥空气的超音速射流H，其露点低于-40℃；所述干燥吸附过程为，采用多个内含分子筛的干燥吸附塔，分子筛总重>200kg，多个干燥吸附塔交替工作和再生，交替时间为3-12分钟。
  17. 根据权利要求14所述的预制锌盐隔膜的制造方法，其特征在于：所述纤维化过程中，进入喷管前的空气预热温度为30-60℃，进入半封闭型腔中粉料F的预热温度为40-220℃。
  18. 根据权利要求14所述的预制锌盐隔膜的制造方法，其特征在于：所述制膜过程，多条连续的粗条或连续厚饼J，其形状由螺杆挤出机挤压头模具决定，连续粗条的直径或连续厚饼的厚度在3-12mm之间；所述卧式冷辊压机的辊面温度为-10-30℃；所述一次减薄后的厚度为0.3-1.5mm；所述加热输送导轨的温度为90-150℃；所述卧式热辊压机的辊面温度为110-160℃；所述二次减薄后的厚度为5-60μm。
  19. 根据权利要求6-10中任一项所述预制锌盐隔膜的制造方法制成的预制锌盐隔膜，其特征在于，包括聚苯硫醚固态隔膜A和位于聚苯硫醚固态隔膜A两侧的上支撑隔膜B、下支撑隔膜F，在上支撑隔膜B、下支撑隔膜F与聚苯硫醚固态隔膜A之间分别填充有包括有机粘接剂和/或无机粘接剂与电解质盐的混合物。
  20. 根据权利要求10-18中任一项所述预制锌盐隔膜的制造方法制成的预制锌盐隔膜，其特征在于，包括聚苯硫醚固态隔膜A和位于聚苯硫醚固态隔膜A两侧的上支撑隔膜B、下支撑隔膜F，在上支撑隔膜B、下支撑隔膜F与聚苯硫醚固态隔膜A之间分别填充有包括有机粘接剂和/或无机粘接剂与电解质盐的混合物，所述聚苯硫醚固态隔膜A是由权利要求3所述的改性聚苯硫醚制成。
  21. 由权利要求19或20所述预制锌盐隔膜制成的备注锌锰二次电池制造方法，其特征在于，将预制锌盐隔膜H置于锰氧化物正极电极和锌负极电极之间，并进行极耳焊接，通过采用叠片机或卷绕机制备得到电池电芯，放入电池壳体 或铝塑膜袋内，封装备用，储存；所述电池壳体或铝塑膜袋上留有能够密封的注液口。
  22. 根据权利要求21所述的备注锌锰二次电池制造方法，其特征在于，所述锰氧化物正极电极为采用半干法技术制造的二氧化锰干法电极，所述的锰氧化物为α-MnO2、β-MnO2、γ-MnO2、δ-MnO2、Mn2O3、Mn3O4、LiMn2O4中的一种或几种的混合物；所述锌负极电极为采用半干法技术制造的锌粉干法电极、锌箔、镀锌铜箔中的一种。
  23. 根据权利要求21所述的备注锌锰二次电池制造方法，其特征在于，在极耳焊接完成后对焊接点进行阻水绝缘保护。
  24. 根据权利要求23所述的备注锌锰二次电池制造方法，其特征在于，焊接点的阻水绝缘保护是采用阻水绝缘胶带包裹、涂氧化铝层或涂抹树脂保护；所述树脂为环氧树脂、酚醛树脂、呋喃树脂、不饱和聚酯中的一种或几种；所述极耳为镍极耳、铜极耳、钛极耳或钼极耳。
  25. 根据权利要求21所述的备注锌锰二次电池制造方法，其特征在于，在得到电池电芯后还采用外部加持机构以增大所述预制锌盐隔膜H、锰氧化物正极电极和锌负极电极间的预紧力，使极间距被控制在50-120μm。
  26. 根据权利要求21所述的备注锌锰二次电池制造方法，其特征在于，所述电池壳体外包装采用阻水阻气耐酸蚀材料，所述阻水阻气耐酸蚀材料为无孔膜。
  27. 根据权利要求26所述的备注锌锰二次电池制造方法，其特征在于，所述无孔膜为双向拉伸聚丙烯薄膜(BOPP)、流延聚丙烯薄膜(CPP)、聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)、聚丙烯(PP)无孔膜中的一种或几种的复合膜。
  28. 根据权利要求21所述的备注锌锰二次电池制造方法，其特征在于，所述锰氧化物正极电极的制造方法，包括以下步骤：首先将二氧化锰与聚四氟乙烯混合后，在聚四氟乙烯的玻璃化转变温度以下，采用干燥的超音速射流气体喷射使聚四氟乙烯的分子链打开与正极材料粉末物理粘连，再纤维化的粉料中喷洒醇溶液，经过密炼、剪切造粒后热辊压为正极膜，再经多次冷辊压将多层正极膜复合成厚度为100-150μm的复合正极自支撑膜，最后将复合正极自支撑 膜与表面涂过胶的喷砂不锈钢箔通过热辊压机复合在一起。
  29. 根据权利要求21所述的备注锌锰二次电池制造方法，其特征在于，所述锌负极电极的制造方法，包括以下步骤：
    将锌粉、导电剂、增韧导电剂、阳离子缓释剂、析氢抑制剂在混料机中混合均匀至粉料A；所述的阳离子缓释剂为具有电负性且遇水体积膨胀的无机粉料；所述的析氢抑制剂是同锌粉在醇水溶剂中能发生还原反应的金属化合物；锌粉、导电剂、增韧导电剂、阳离子缓释剂、聚四氟乙烯、析氢抑制剂粉体的重量百分比:60％-90％：1％-10％：1％-10％：1％-10％：3％-15％：0.1％-5％；
    将聚四氟乙烯粉体和粉料A在混料机中混合均匀至粉料B；混合过程在聚四氟乙烯(PTFE)呈玻璃态的温度条件下进行；
    所述粉料B和醇水混合溶剂在球磨设备中，通过球磨珠在高速转动中不断摩擦使得PTFE拉丝呈网状结构，粉料B中的聚四氟乙烯的分子链延展打开，同粉料A中的粉体形成物理粘连，析氢抑制剂与锌粉表面发生还原反应，待上述过程结束后，过滤获得胶团C；
    胶团C经密炼后形成均匀胶团，再经过剪切造粒后制成大小均一的毫米级颗粒料E；
    颗粒料E经卧式热辊压机热压制成负极膜F，并采用多孔离型纸做支撑托带完成收卷，贴覆离型纸的负极膜F整卷进行干燥，排除部分溶剂；
    采用热压复合工艺，将揭掉离型纸后的半干燥负极膜F热复合在涂胶不锈钢箔的两面制成电极。
  30. 根据权利要求29所述的备注锌锰二次电池制造方法，其特征在于，所述锌粉为粒径在5-20μm的粉末状颗粒；所述导电剂为super-P、ECP中的一种或两种，所述的增韧导电剂为人造石墨、高纯石墨中的一种或两种的混合物。
  31. 根据权利要求29所述的备注锌锰二次电池制造方法，其特征在于，所述阳离子缓释剂为膨润土、蒙脱石粉、伊利石粉、高岭土粉、埃洛石粉中的一种或几种；所述析氢抑制剂为氯化铟、氯化铜、硫酸铟、硫酸铜中的一种或几种。
  32. 根据权利要求29所述的备注锌锰二次电池制造方法，其特征在于，所述醇水混合溶剂为水和异丙醇、丙二醇或乙醇的混合溶剂，水与醇的体积百分 比为：40％-80％：20％-60％；所述的均匀胶团的固含量为40％-60％。
  33. 根据权利要求29所述的备注锌锰二次电池制造方法，其特征在于，所述颗粒料E经卧式热辊压机辊压一次达到负极膜F的厚度为90-200μm，热辊压温度为55-95℃。
  34. 根据权利要求29所述的备注锌锰二次电池制造方法，其特征在于，半干燥负极膜F与不锈钢箔热复合时，涂胶不锈钢箔被两张已揭掉离型纸的负极膜F夹在中间，经同速放卷，进入两个相对转动的卧式热辊压机，辊压温度为30-120℃，通过调节辊缝宽度，控制压力，使得负极膜F刚好能够复合在涂胶不锈钢箔上即可，避免因辊压力过大导致负极膜F形变过大拉断不锈钢箔。
  35. 根据权利要求29所述的备注锌锰二次电池制造方法，其特征在于，所述的涂胶不锈钢箔为采用凹版印刷机将高导电浆料印刷在不锈钢箔的两面，不锈钢箔表面在涂胶前需经过喷砂处理，除掉表面轧制油，高导电浆料由高纯石墨、不亲水粘接剂和非水溶剂组成。
  36. 根据权利要求21-29任一项所述的备注锌锰二次电池制造方法制成的备注锌锰二次电池，其特征在于，由锰氧化物正极电极、锌负极电极、三层预制锌盐隔膜H和带有可密封注液口的电池壳体或铝塑膜袋组成，锰氧化物正极电极、锌负极电极和三层预制锌盐隔膜H经极耳焊接后，置于电池壳体或铝塑膜袋内。
  37. 根据权利要求36所述的备注锌锰二次电池的应用方法，其特征在于，所述备注锌锰二次电池在存储运输过程中，不需要注液；在投入使用前，在电池中注入纯水、海水或稀电解液；优选地，所述的稀电解液为浓度为0.01mol/L到1mol/L的硫酸锌、硫酸钠、硫酸镁、氯化钠、三氟甲烷磺酸锌中的一种或几种的盐溶液，其溶剂为水、乙醇、甲醇、丙二醇、异丙醇、丙三醇中的一种或几种的混合物；优选地，注入液体的量为1-20mL/Ah。
  38. 根据权利要求36所述的备注锌锰二次电池的化成方法，其特征在于，在电池化成过程中，首先在所述二次电池中注入仅以水为溶剂的电解液，以电流密度为1-20mA/g的小电流化成进行一次放电，再进行充放电0-40圈后，在电池放电状态下，注入有机溶剂，再进行真空封装，所述有机溶剂为与水混合后能够降低水的凝固点的有机溶剂，所述的水溶液电解液和有机溶剂的体积比 为5:0.3-5。
  39. 根据权利要求37所述的备注锌锰二次电池的化成方法，其特征在于，所述以水为溶剂的电解液是2-3mol/L的三氟甲磺酸锌水溶液、2-3mol/L的硫酸锌水溶液或2-3mol/L的氯化锌水溶液；注液量为3-10mL/Ah。
  40. 根据权利要求37所述的备注锌锰二次电池的化成方法，其特征在于，所述有机溶剂为醇、二甲基亚砜、碳酸丙烯酯、乙腈。
  41. 根据权利要求39所述的备注锌锰二次电池的化成方法，其特征在于，所述的醇为甲醇、异丙醇、乙二醇、丙二醇、丙三醇中的一种或几种的混合醇。
PCT/CN2024/086497 2023-04-13 2024-04-08 改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法 Ceased WO2024212909A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/860,698 US12444807B2 (en) 2023-04-13 2024-04-08 Modified polyphenylene sulfide (PPS) and PPS modification method, PPS solid separator, prefabricated zinc salt separator and manufacturing method thereof, to-be-filled zinc-manganese secondary battery, and manufacturing and application methods thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202310393324.5A CN117264212A (zh) 2023-04-13 2023-04-13 改性聚苯硫醚、固态隔膜、安时级锌锰二次电池及其制造及化成方法
CN202310393324.5 2023-04-13
CN202410046169.4A CN117878527A (zh) 2024-01-12 2024-01-12 预制锌盐隔膜、备注锌锰二次电池及其制造方法
CN202410046169.4 2024-01-12

Publications (1)

Publication Number Publication Date
WO2024212909A1 true WO2024212909A1 (zh) 2024-10-17

Family

ID=93058721

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/086497 Ceased WO2024212909A1 (zh) 2023-04-13 2024-04-08 改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法

Country Status (2)

Country Link
US (1) US12444807B2 (zh)
WO (1) WO2024212909A1 (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012033443A (ja) * 2010-08-03 2012-02-16 Fujifilm Corp 光電変換素子及び光電気化学電池、それに用いられる色素
CN106450424A (zh) * 2016-10-24 2017-02-22 天津新动源科技有限公司 一种聚合物复合固态电解质及其制备方法和应用
US20200028147A1 (en) * 2018-07-18 2020-01-23 Nanotek Instruments, Inc. Method of improving fast-chargeability of a lithium-ion battery
CN111864272A (zh) * 2020-06-09 2020-10-30 江苏大学 一种高安全性高体积能量密度准固态锂离子电池及其制造方法
CN113078372A (zh) * 2021-04-09 2021-07-06 江苏大学 锌离子固态电解质及其在准固态锌离子电池中的应用及制备方法
CN115588784A (zh) * 2022-10-08 2023-01-10 江苏大学 一种安时级锌锰二次电池及其制造方法
CN117264212A (zh) * 2023-04-13 2023-12-22 江苏大学 改性聚苯硫醚、固态隔膜、安时级锌锰二次电池及其制造及化成方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617387A (en) * 1969-02-20 1971-11-02 Union Carbide Corp Battery construction having cell components completely internally bonded with adhesive
JP4900365B2 (ja) * 2007-11-08 2012-03-21 東レ株式会社 ポリフェニレンスルフィド樹脂の製造方法
CN102263298B (zh) * 2011-06-22 2014-09-24 广东博特动力能源有限公司 一种锌镍二次电池及其制备方法
CN107112493B (zh) * 2015-01-29 2020-07-24 三洋电机株式会社 非水电解质二次电池
US12431532B2 (en) * 2017-06-01 2025-09-30 Lg Energy Solution, Ltd. Electrolyte composition, secondary cell, and method for manufacturing electrolyte sheet
KR102369524B1 (ko) * 2017-11-21 2022-03-03 아사히 가세이 가부시키가이샤 축전 디바이스용 세퍼레이터 및 축전 디바이스
US12230765B2 (en) * 2018-02-26 2025-02-18 Zeon Corporation Method of producing laminate for secondary battery
CN109761265B (zh) * 2019-01-23 2020-08-14 宁德新能源科技有限公司 固态电解质及其制备方法与包含其的电化学装置及电子装置
JPWO2020235588A1 (zh) * 2019-05-20 2020-11-26
WO2021212050A1 (en) * 2020-04-17 2021-10-21 Urban Electric Power Inc. Improving zinc-manganese dioxide battery performance through interlayers
CN114072933A (zh) * 2020-05-26 2022-02-18 宁德新能源科技有限公司 正极及使用其的电化学装置和电子装置
CN112898569B (zh) 2021-01-29 2022-06-03 江苏大学 表面功能化的聚苯硫醚、固液双相电解质及制备方法
CN117957697A (zh) * 2021-09-15 2024-04-30 大日本印刷株式会社 蓄电器件用外包装材料、其制造方法、膜和蓄电器件
CN116825941B (zh) 2022-04-01 2024-04-09 江苏大学 锌锰准固态液流电池的氧化锰基正极及其半干法电极制造方法
CN116826299B (zh) 2022-04-26 2024-07-30 江苏大学 正负极侧异性的固态隔膜、制备方法、用途及水系金属准固态液流电池
CN116130672B (zh) 2022-10-08 2024-05-14 江苏大学 锌锰准固态液流电池的锌粉负极及其半干法电极制造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012033443A (ja) * 2010-08-03 2012-02-16 Fujifilm Corp 光電変換素子及び光電気化学電池、それに用いられる色素
CN106450424A (zh) * 2016-10-24 2017-02-22 天津新动源科技有限公司 一种聚合物复合固态电解质及其制备方法和应用
US20200028147A1 (en) * 2018-07-18 2020-01-23 Nanotek Instruments, Inc. Method of improving fast-chargeability of a lithium-ion battery
CN111864272A (zh) * 2020-06-09 2020-10-30 江苏大学 一种高安全性高体积能量密度准固态锂离子电池及其制造方法
CN113078372A (zh) * 2021-04-09 2021-07-06 江苏大学 锌离子固态电解质及其在准固态锌离子电池中的应用及制备方法
CN115588784A (zh) * 2022-10-08 2023-01-10 江苏大学 一种安时级锌锰二次电池及其制造方法
CN117264212A (zh) * 2023-04-13 2023-12-22 江苏大学 改性聚苯硫醚、固态隔膜、安时级锌锰二次电池及其制造及化成方法

Also Published As

Publication number Publication date
US12444807B2 (en) 2025-10-14
US20250174824A1 (en) 2025-05-29

Similar Documents

Publication Publication Date Title
CN112290081B (zh) 高能量密度准固态钠离子电池的制造方法
CN115588784B (zh) 一种安时级锌锰二次电池及其制造方法
CN111554883B (zh) 一种基于干法制备电极膜的预锂化方法
CN103560252B (zh) 一种柔性易回收铅酸蓄电池芯及其制备方法
WO2023186165A1 (zh) 一种钠离子电池及其制备方法和应用
CN108878806B (zh) 一种大容量双袋式锌镍二次电池及其制备方法
CN211907608U (zh) 锂离子电池结构
CN114597581B (zh) 一种改性隔膜、制备方法及在锂离子电池中的应用
CN101188310A (zh) 一种磷酸铁锂铝壳圆柱电池及其制作工艺
CN114497463A (zh) 一种锂离子电池负极连续补锂的方法
CN101281820A (zh) 一种层叠式超级电容器及其制造方法
CN115172757B (zh) 一种集流体及其制备方法和二次电池及装置
CN113991074A (zh) 一种超低温锰酸锂电池
CN114552029A (zh) 一种用于长寿命锌碘电池的沸石基离子交换涂层
CN114551854A (zh) 一种高能量密度和长循环寿命水系锌基二次电池
EP4362123A1 (en) Negative electrode sheet and battery applying same
CN116001332A (zh) 固态隔膜的制造设备及方法
CN116314610A (zh) 一种二次电池和用电设备
CN101183731A (zh) 一种磷酸铁锂铝壳10安时圆柱电池及其制作工艺
CN116130672B (zh) 锌锰准固态液流电池的锌粉负极及其半干法电极制造方法
CN116825941B (zh) 锌锰准固态液流电池的氧化锰基正极及其半干法电极制造方法
CN102005562B (zh) 一种锂离子电池及其制作方法
EP4156318A1 (en) Method for treating negative electrode plate, and sodium metal negative electrode plate and related apparatus
WO2024212909A1 (zh) 改性聚苯硫醚及其改性方法、聚苯硫醚固态隔膜、预制锌盐隔膜及其制造方法、备注锌锰二次电池及其制造、及应用方法
CN220400625U (zh) 一种高能量密度混合型钠离子电池正极片

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 18860698

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24788012

Country of ref document: EP

Kind code of ref document: A1

WWP Wipo information: published in national office

Ref document number: 18860698

Country of ref document: US

WWG Wipo information: grant in national office

Ref document number: 18860698

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 24788012

Country of ref document: EP

Kind code of ref document: A1