WO2017020860A1 - Batterie, ensemble batterie et source d'alimentation non interruptible - Google Patents

Batterie, ensemble batterie et source d'alimentation non interruptible Download PDF

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Publication number
WO2017020860A1
WO2017020860A1 PCT/CN2016/093598 CN2016093598W WO2017020860A1 WO 2017020860 A1 WO2017020860 A1 WO 2017020860A1 CN 2016093598 W CN2016093598 W CN 2016093598W WO 2017020860 A1 WO2017020860 A1 WO 2017020860A1
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WIPO (PCT)
Prior art keywords
negative electrode
positive electrode
battery
zinc
electrolyte
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PCT/CN2016/093598
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English (en)
Chinese (zh)
Inventor
陈璞
李如飞
罗云峰
刘洋
萨阿德萨迈赫·M
罗小松
刘新永
Original Assignee
苏州宝时得电动工具有限公司
陈璞
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Publication date
Priority claimed from CN201510474584.0A external-priority patent/CN106450509A/zh
Priority claimed from CN201510736618.9A external-priority patent/CN106654274A/zh
Application filed by 苏州宝时得电动工具有限公司, 陈璞 filed Critical 苏州宝时得电动工具有限公司
Publication of WO2017020860A1 publication Critical patent/WO2017020860A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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 invention belongs to the field of electrochemical energy storage, and in particular relates to a battery.
  • the invention also relates to a battery pack comprising a plurality of batteries.
  • the invention also relates to an uninterruptible power supply.
  • the lead-acid battery has been in existence for more than 100 years and has mature battery technology, occupying an absolute market share in the energy storage fields such as automobile starter batteries, electric bicycles and UPS.
  • the lead-acid battery has a low cycle life and a relatively low energy density, it has the advantages of very low price and very high cost performance. Therefore, in recent years, nickel-metal hydride batteries, lithium-ion batteries, sodium-sulfur batteries, and liquid flow batteries have failed to replace lead-acid batteries in the field of energy storage.
  • the positive electrode of the secondary battery is capable of undergoing a reversible elution-embedding reaction based on the first metal ion
  • the negative electrode is capable of undergoing a reversible reduction deposition-oxidation dissolution reaction based on the second metal ion, the electrolyte containing the first metal participating in the positive electrode extraction-embedding reaction Ions and a second metal ion that participates in the negative electrode deposition-dissolution reaction.
  • the electrolyte of this type of battery is an aqueous solution, and there is no safety hazard similar to the organic electrolyte in a lithium ion battery, and it is environmentally friendly, low in cost, and high in energy density. Therefore, this type of battery is very promising as a next-generation energy storage battery to replace lead-acid batteries, which has great application value.
  • the second metal ion of the battery of this type may be zinc ion.
  • the negative electrode active material is metal zinc.
  • such a negative electrode active material has problems such as dendrite when charged and discharged in an aqueous solution, thereby causing cycle performance and charge and discharge capacity of the battery. affected. Therefore, the prior art needs further improvement.
  • the technical problem to be solved by the present invention is to provide a battery in which the dendrite problem of the battery negative electrode is significantly improved, thereby improving the cycle life of the battery and improving the electrochemical performance of the battery.
  • a battery including a positive electrode, a negative electrode, and an aqueous electrolyte, the positive electrode including a positive electrode active material and a positive electrode current collector
  • the aqueous electrolyte includes a first metal ion and/or a second metal ion, the first metal ion being reversibly detachable-embedded in the positive electrode during charging and discharging, and the second metal ion being in a charging process Reducing and depositing the negative electrode as a second metal, the second metal is oxidatively dissolved into a second metal ion during discharge;
  • the negative electrode includes a negative electrode material having a porous structure, the negative electrode material including a zinc active material and a negative electrode Binder.
  • the anode further includes a cathode current collector having a mesh structure, and the anode material is supported on the anode current collector.
  • the pore size of the mesh of the anode current collector ranges from 0.3 mm to 1.5 mm, and the thickness of the anode current collector ranges from 0.01 mm to 0.5 mm.
  • the zinc active material comprises zinc and a zinc-containing compound
  • the zinc-containing compound comprises at least one of zinc oxide, zinc hydroxide and a zinc salt, wherein the zinc-containing compound accounts for 100% of the mass of the negative electrode material.
  • the content of the fraction is 0-50%.
  • the method for preparing the negative electrode comprises the steps of: dispersing zinc and/or a zinc-containing compound and a negative electrode binder in water, stirring uniformly to obtain a negative electrode slurry; and coating the negative electrode slurry on the negative electrode set Fluid, dry, rolling, shearing; the obtained zinc negative electrode and nickel positive electrode are placed in a 2-7 mol/L potassium hydroxide solution, charged at a constant voltage of 2.1 V, a constant current of 0.2 C, and charged until the charging capacity is reached.
  • the theoretical capacity of the zinc oxide is from 100% to 150%, and the zinc negative electrode is washed to neutral.
  • the negative electrode binder accounts for no more than 7% by mass of the negative electrode material.
  • the negative electrode binder comprises polyvinyl alcohol (PVA), hydroxypropyl methylcellulose (HPMC), polyacrylamide (PAM), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF).
  • PVA polyvinyl alcohol
  • HPMC hydroxypropyl methylcellulose
  • PAM polyacrylamide
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • the anode material further comprises an additive, the additive comprising no more than 5% by mass of the anode material.
  • the additive is selected from the group consisting of oxides or hydroxides or salts of lead, indium, antimony, calcium.
  • the anode material further comprises a conductive agent, and the conductive agent accounts for no more than 5% by mass of the anode material.
  • the conductive agent is one or more selected from the group consisting of metallic nickel, metallic copper, and conductive ceramics.
  • the conductive agent is one or more selected from the group consisting of activated carbon, graphite, carbon black, carbon nanotubes, graphene and oxides thereof.
  • the conductive agent is selected from the group consisting of a mixture of activated carbon and graphite or a mixture of activated carbon and carbon nanotubes.
  • the material of the anode current collector comprises copper, lead, copper, iron or stainless steel plated with lead, indium, antimony or tin.
  • the first metal ion comprises a lithium ion, a sodium ion or a magnesium ion.
  • the second metal ion comprises zinc ions.
  • the aqueous electrolyte has a pH of 3-7.
  • the present invention also provides a battery pack comprising a plurality of batteries as described above.
  • the present invention also provides an uninterruptible power supply comprising the battery as described above.
  • the invention has the beneficial effects that the battery provided by the invention has a porous negative electrode, and the porous negative electrode has a large surface area, thereby reducing the polarization of the negative electrode during charging and reducing the formation of dendrites.
  • the porous negative electrode can store a large amount of electrolyte inside the structure, and the internal liquid-solid phase interface area is much larger than the surface area, so that the reduction of zinc ions is more carried out inside the porous negative electrode, thereby further reducing the formation of dendrites, thereby Increase the cycle life of the battery to improve the electrochemical performance and safety of the battery.
  • Another technical problem to be solved by the present invention is to provide an electrolyte capable of suppressing corrosion of the negative electrode and improving the electrochemical performance of the battery.
  • an electrolyte comprising: a solvent, the solvent is water; and a second metal ion, the second metal ion is in a charging process
  • the anode is reduced to be deposited as a second metal, and the second metal is reversibly oxidized to dissolve into a second metal ion during discharge;
  • the electrolyte further includes an ionic liquid.
  • the cation constituting the ionic liquid is an imidazole cation, a quaternary ammonium cation, a quaternary phosphonium cation or a pyrrole cation.
  • the imidazole cation is 1-butyl-3-methylimidazolium cation or 1- Ethyl-3-methylimidazolium cation.
  • the anion constituting the ionic liquid is selected from the group consisting of a hexafluorophosphate ion, a hydrogen sulfate ion, a dicyanamide ion, a chloride ion, a tetrafluoroborate ion, a methanesulfonate ion, and an ethylsulfonate ion.
  • a hexafluorophosphate ion a hydrogen sulfate ion
  • a dicyanamide ion a chloride ion
  • a tetrafluoroborate ion a methanesulfonate ion
  • methanesulfonate ion a methanesulfonate ion
  • an ethylsulfonate ion is selected from the group consisting of a hexafluorophosphate ion, a hydrogen sulfate ion
  • the ionic liquid accounts for 0.1% to 50% by mass of the electrolyte.
  • the second metal ion comprises one of zinc ion, iron ion, manganese ion, chromium ion, aluminum ion, copper ion and nickel ion.
  • the electrolyte further includes a first metal ion capable of reversibly eluting-embedding at the positive electrode during charge and discharge.
  • the first metal ion comprises one of a lithium ion, a sodium ion, an aluminum ion, and a magnesium ion.
  • the electrolyte has a pH in the range of 1-8.
  • Another technical problem to be solved by the present invention is to provide a battery having better battery performance to make it more suitable for use in energy equipment.
  • a battery comprising a positive electrode, a negative electrode and an electrolyte, and the electrolyte is the above electrolyte.
  • the invention has the beneficial effects that the electrolyte containing the additive ionic liquid has an improved electrochemical window, better ionic conductivity, improved low temperature performance, and reduced water evaporation rate.
  • the electrolyte solution having the electrolyte not only suppresses corrosion, dendrites, and gas generation of the anode, but also suppresses corrosion and gas generation of the cathode, thereby improving the cycle performance of the battery and exerting better battery performance.
  • the invention also provides a battery capable of improving the corrosion problem of the positive electrode conductive agent of the battery, thereby improving the floating life of the battery.
  • the technical solution provided by the present invention is: a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode material, the positive electrode material comprising a positive electrode binder, a positive electrode conductive agent and a positive electrode active material
  • the positive active material is capable of reversibly extracting-embeding a first metal ion
  • the electrolyte includes solvent water and an electrolyte salt, the electrolyte salt being capable of at least ionizing the first metal ion and the second metal ion; a metal ion capable of reversible extraction-embedding in the positive electrode during charge and discharge;
  • the second metal ion is selectively deposited as a second metal in the negative electrode during charging, the second metal is oxidatively dissolved into a second metal ion during discharge;
  • the positive electrode binder comprises an acrylonitrile multicomponent copolymer, At least one of polyacrylic acid and hydroxypropylmethyl
  • the positive electrode binder accounts for 1%-10% by mass of the positive electrode material.
  • the positive electrode binder further comprises one of carboxymethyl cellulose, styrene-butadiene rubber, carboxymethyl cellulose and styrene-butadiene rubber, and derivatives of carboxymethyl cellulose and styrene-butadiene rubber.
  • the positive electrode binder further includes at least one of titanium oxide, silicon oxide and aluminum oxide.
  • the acrylonitrile multicomponent copolymer is from 10% to 90% by weight in the positive electrode binder.
  • the weight percentage of the acrylonitrile multicomponent copolymer in the positive electrode binder is 50% to 75%.
  • the positive electrode conductive agent is at least one selected from the group consisting of graphite, carbon nanotubes, carbon black, and activated carbon.
  • the electrolyte has a pH of from 3 to 7.
  • the anion in the electrolyte comprises one or more of a sulfate ion, a chloride ion, an acetate ion, a formate ion, a phosphate ion or an alkylsulfonate ion.
  • the first metal ion is selected from the group consisting of lithium ion, sodium ion or magnesium ion.
  • the second metal ion is manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
  • the positive active material is one or more selected from the group consisting of LiMn 2 O 4 , LiFePO 4 or LiCoO 2 .
  • the present invention also provides a battery pack comprising a plurality of batteries as described above.
  • the present invention also provides an uninterruptible power supply comprising the battery as described above.
  • the positive electrode binder used in the battery of the invention improves the hydrophilicity of the positive electrode, reduces the interface resistance between the positive electrode and the electrolyte, and reduces the internal resistance of the battery; on the other hand, the positive electrode binder The positive electrode active material is contacted with the conductive agent to inhibit the loss of the conductive agent, and the self-discharge of the battery is reduced, so that the battery has a high floating life.
  • the present embodiment provides a battery including a positive electrode, a negative electrode, and an aqueous electrolyte.
  • the positive electrode includes a positive electrode active material and a positive electrode current collector; the aqueous electrolyte solution includes a first metal ion and/or a second metal ion, and the first metal ion is charged.
  • the positive electrode can be reversibly extracted-embedded, the second metal ion is reduced and deposited into a second metal during charging, and the second metal is oxidized and dissolved into a second metal ion during discharge;
  • the negative electrode includes a negative electrode having a porous structure.
  • the substance, the negative electrode material includes a zinc active material and a negative electrode binder.
  • the positive active material has a spinel structure, a layered structure or an olivine structure.
  • the positive electrode active material may be a compound capable of reversibly deintercalating-intercalating lithium ion in a layered structure conforming to the general formula Li 1+x M y M′ z M′′ c O 2+n , wherein ⁇ 1 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ c ⁇ 1, -0.2 ⁇ n ⁇ 0.2, M, M', M" are respectively selected from Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr At least one of Si, Si or Al.
  • the positive electrode active material contains LiCoO 2 .
  • LiMn 2 O 4 can not represent the general formula of "manganese manganate" which is widely used, but should be of the general formula Li 1+x
  • the Mn y M z O k is broadly included, and variously modified LiMn 2 O 4 positive electrode active materials are widely included.
  • LiFePO 4 and LiCoO 2 should also be broadly understood to include modifications through various doping, cladding, etc., which are in accordance with Li x M 1-y M' y (XO 4 ) n and Li 1+, respectively. a positive electrode active material of x M y M' z M" c O 2+n .
  • the positive electrode active material is a substance capable of reversible elution-intercalation of lithium ions
  • a compound such as LiMn 2 O 4 , LiFePO 4 , LiCoO 2 , LiM x PO 4 , LiM x SiO y (where M is a variable valence metal) may preferably be selected. .
  • the positive electrode active material is LiMn 2 O 4 .
  • LiMn 2 O 4 is considered to be one of the most promising cathode materials because of its low cost, sufficient raw materials, environmental friendliness, and good safety.
  • compounds that can be extracted - intercalated with sodium ions can be extracted - compounds intercalated with magnesium ions (such as MgM x O y (where M is a metal, 0.5 ⁇ x ⁇ 3, 2 ⁇ y ⁇ 6 )) and a compound having a similar function capable of eluting-embedding ions or functional groups can be used as the positive electrode active material of the battery of the present invention. Therefore, the present invention is not limited to a lithium ion battery.
  • a positive electrode conductive agent and a positive electrode binder are usually added to improve the performance of the positive electrode.
  • the positive electrode conductive agent can reduce the electrical resistance of the entire positive electrode while enhancing the conductive path between the positive electrode material particles. There are various ways to select the positive electrode conductive agent of the present invention.
  • the positive electrode conductive agent is selected from one or more of a conductive polymer, a conductive oxide, a conductive ceramic, activated carbon, graphene, carbon black, graphite, carbon fiber, metal fiber, metal powder, and metal foil.
  • the positive electrode conductive agent accounts for 1% to 15% by mass of the positive electrode material.
  • the positive electrode conductive agent is graphite, and the positive electrode conductive agent accounts for 10% to 14% by mass of the positive electrode material.
  • the positive electrode conductive agent is at least one selected from the group consisting of graphite, carbon nanotubes, carbon black, and activated carbon.
  • Carbon black includes, but is not limited to, acetylene black and Super-P.
  • Graphite is flake graphite or spheroidal graphite.
  • flake graphite includes SFG6 and SFG15; and spherical graphite includes KS6 and KS15. More preferably, the graphite is flake graphite, and the flake graphite has anisotropy, so that it has good corrosion resistance, thereby improving the self-discharge and floatation performance of the positive electrode.
  • the positive electrode conductive agent accounts for 6%-15% of the mass percentage of the positive electrode material
  • the positive electrode active material accounts for 80-90% of the mass percentage of the positive electrode material. Therefore, the positive electrode has a high capacity while ensuring excellent conductivity of the positive electrode material.
  • the positive electrode binder facilitates uniform bonding of the positive electrode active material and the conductive agent, and is maintained on the current collector to enhance electronic contact between the positive electrode active material and the positive electrode current collector. Thereby processing forms a positive electrode.
  • the positive electrode binder of the present invention has a variety of options.
  • the positive electrode binder may be selected from the group consisting of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimide, polyester, polyether, fluorinated polymer, polydivinyl polyethylene glycol, poly One of ethylene glycol diacrylate, polyethylene glycol dimethacrylate, or a mixture and derivative of the above polymers. More preferably, the positive electrode binder is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) or styrene butadiene rubber (SBR).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • SBR styrene butadiene rubber
  • the positive electrode binder includes at least one of an acrylonitrile multicomponent copolymer (LA133), polyacrylic acid (PAA), and hydroxypropylmethylcellulose (HPMC).
  • LA133 acrylonitrile multicomponent copolymer
  • PAA polyacrylic acid
  • HPMC hydroxypropylmethylcellulose
  • the battery provided by the invention is a water-based battery, and the working voltage range of the battery is generally 1.4-2.1V.
  • the positive electrode conductive agent is oxidized at a high voltage, which causes gas to be generated inside the battery, and the gas hinders the positive electrode from being aqueous electrolyte. Wetting increases the interfacial impedance between the positive electrode and the electrolyte.
  • the positive electrode binder provided in the second method can mainly improve the hydrophilicity of the positive electrode, reduce the interface resistance between the positive electrode and the aqueous electrolyte, and reduce the internal resistance of the battery.
  • the positive electrode binder accounts for 1% to 10% by mass of the positive electrode material. Such a setting not only ensures an effective combination of the positive electrode active material and the positive electrode conductive agent, but also does not affect the energy density of the battery.
  • the positive electrode binder comprises, in addition to at least one of LA133, PAA and HPMC, the positive electrode binder further comprises carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), carboxy.
  • CMC carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • Derivatives of styrene butadiene rubber include, but are not limited to, hydrophilically modified styrene butadiene rubber (PSBR).
  • the positive electrode binder comprises LA133 and CMC; in another embodiment, the positive electrode binder comprises LA133, CMC and SBR; in another embodiment, the positive electrode binder comprises LA133, CMC and PSBR .
  • LA133 is often used as a negative electrode binder for lithium ion batteries because of its strong bonding property, thereby suppressing the occurrence of powder drop during charging and discharging of the negative electrode.
  • LA133 is used as a positive electrode binder for an aqueous battery, which mainly suppresses loss of the positive electrode conductive agent, reduces self-discharge, and improves battery float life.
  • the positive electrode binder comprises HPMC and SBR.
  • the material of the cathode current collector is selected from one of a carbon-based material, a metal or an alloy.
  • the carbon-based material is selected from the group consisting of glassy carbon, graphite foil, graphite flakes, foamed carbon, carbon felt, carbon cloth, and carbon fiber.
  • the cathode current collector comprises a carrier and a graphite foil coated on the carrier.
  • the alloy includes one of stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or passivated.
  • Stainless steel includes stainless steel mesh, stainless steel foil, and stainless steel models include, but are not limited to, one of stainless steel 304 or stainless steel 316 or stainless steel 316L.
  • the chemical passivation treatment includes oxidizing the cathode current collector by an oxidizing agent to form a passivation film on the surface of the cathode current collector.
  • the principle of oxidant selection is that the oxidant can form a passivation film on the surface of the positive current collector without dissolving the positive current collector.
  • the oxidizing agent is selected from, but not limited to, concentrated nitric acid or sorghum sulfate (Ce(SO 4 ) 2 ).
  • the electrochemical passivation treatment comprises electrochemically oxidizing the cathode current collector or charging and discharging the battery containing the cathode current collector to form a passivation film on the surface of the cathode current collector.
  • the positive electrode further includes a composite current collector supporting the positive electrode active material, and the composite current collector includes a positive electrode current collector and a conductive film coated on the positive electrode current collector.
  • the conductive film is bonded to the positive current collector by hot press lamination, vacuuming or spraying.
  • the positive electrode binder is selected from the group consisting of a mixture of styrene butadiene rubber and sodium carboxymethyl cellulose (CMC), and the current collector is selected from a stainless steel wire mesh coated with a conductive film.
  • CMC carboxymethyl cellulose
  • the sheared negative electrode is externalized to reduce the zinc-containing compound to zinc.
  • the anode material supported on the anode current collector becomes porous during the reduction process, and has a large specific surface area.
  • the zinc-containing compound in the negative electrode material is all reduced to zinc, that is, the mass content of the zinc-containing compound is 0; but in general, it is difficult to achieve a state of 100%.
  • the value of the charge capacity is monitored during the formation to determine the degree of formation.
  • the zinc-containing compound may have a certain residual amount, that is, the mass percentage of the zinc-containing compound in the negative electrode material of the negative electrode after the final formation. The content is 0-50%.
  • the mass percentage of the zinc-containing compound in the negative electrode material can be out of the range of 50% by controlling the formation time, but it is still within the scope of the present invention if it is merely avoided.
  • the density of zinc oxide is nearly 30% smaller than that of zinc.
  • the volume of zinc oxide of the same mass is much larger than the volume of zinc.
  • the zinc source is made of zinc and/or zinc-containing compound, and then the porous anode is prepared.
  • the formation of the zinc-containing compound is reduced to zinc, and the surface area of the obtained porous zinc negative electrode is remarkably larger than that of the zinc negative electrode which has not been formed. Therefore, the polarization of the negative electrode during charging can be further reduced, and the formation of dendrites can be reduced.
  • the additive accounts for no more than 5% by mass of the negative electrode material.
  • the additive is selected from one or more of the oxides or hydroxides of lead, indium, antimony, calcium. In a preferred embodiment, the additive utilizes both lead oxide, indium oxide, and calcium hydroxide.
  • the anode material further comprises a conductive agent, and the conductive agent can increase the conductivity of the anode material, thereby reducing the internal resistance of the zinc anode.
  • the conductive agent accounts for no more than 5% by mass of the negative electrode material.
  • the conductive agent is one or more selected from the group consisting of metallic nickel, metallic copper, and conductive ceramics.
  • the conductive agent is a carbon-based material having a high specific surface area, so that not only the conductivity of the negative electrode material can be improved, but also the negative electrode material can be further made porous.
  • the carbon-based material includes one or more of activated carbon, graphite, carbon black, carbon nanotubes, graphene, and oxides thereof.
  • carbon black includes acetylene black and Super P.
  • the anode binder is selected from the group consisting of polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • HPMC hydroxypropylmethylcellulose
  • PVA polyvinyl alcohol
  • PAM polyacrylamide
  • CMC carboxymethylcellulose
  • SBR styrene butadiene rubber
  • the anode further includes a cathode current collector having a mesh structure, and the anode material is supported on the anode current collector.
  • the manner in which the anode slurry is coated on the anode current collector in the preparation of the anode is not particularly limited, and in a specific embodiment, the anode slurry is coated on the anode current collector by slurry application.
  • the first metal ion is selected from the group consisting of lithium ions, sodium ions or magnesium ions. More preferably, the first metal ion is a lithium ion.
  • the aqueous electrolyte further includes a second metal ion, and the second metal ion is reduced and deposited as a second metal in the negative electrode during charging, and the second metal is oxidized and dissolved into the second metal ion during the discharging process.
  • the second metal ion is selected from the group consisting of manganese ions, iron ions, copper ions, zinc Ion, chromium ion, nickel ion, tin ion or lead ion; preferably zinc ion.
  • the battery is first charged for charging.
  • the battery may be either charged or discharged for the first time.
  • the first metal ion is different from the second metal ion.
  • the aqueous electrolyte includes both lithium ions and zinc ions. During charge and discharge, lithium ions are intercalated-extracted at the positive electrode, and zinc ions are deposited-dissolved at the negative electrode.
  • the alkyl sulfonate ion is a methanesulfonate ion.
  • the use of the methylsulfonate ion further enhances the solubility of the first metal ion and the second metal ion in the electrolyte, and the cost thereof is low.
  • the concentration of the first metal ion is 0.1 to 10 mol/L.
  • the concentration of the second metal ion is 0.5 to 15 mol/L.
  • the present invention also provides a battery pack comprising a plurality of the above-described batteries, in particular, a battery pack is produced by connecting two or more batteries in series, in parallel, or a combination thereof.
  • the capacity and voltage of the battery pack can be freely adjusted by series and/or parallel connection of the batteries.
  • Root The battery provided by the present invention or the battery pack constructed of the battery can be used as a power source for vehicles and transportation means such as trains, and as a fixed/installable power source such as an uninterruptible power source.
  • the second electrolyte ionizes the generated second metal ion in the electrolyte, and can be reduced and deposited as a second metal in the negative electrode during charging, and the second metal is reversibly oxidized into the second metal ion during the discharging process. That is, when the battery is charged, the second metal ion in the electrolyte is reduced to the second metal and deposited on the negative electrode; when the battery is discharged, the first metal is reoxidized to become the second metal ion and is eluted from the negative electrode to enter the electrolyte. .
  • the second metal ion comprises one of zinc ions, iron ions, manganese ions, chromium ions, aluminum ions, copper ions or nickel ions. More preferably, the second metal ion is a zinc ion.
  • the second anion is selected from one or more of a sulfate ion, a chloride ion, a bromide ion, an acetate ion, a nitrate ion, a phosphate ion, a formate ion, and an alkylsulfonate ion. .
  • An additive ionic liquid is also included in the electrolyte.
  • An ionic liquid, or ionic liquid refers to a liquid that is composed entirely of ions.
  • the ionic liquid according to the present invention refers to a salt which is liquid at room temperature or near room temperature and which is completely composed of an anion and a cation, and is also called a room temperature ionic liquid, an organic ionic liquid, a low temperature molten salt or a room temperature molten salt.
  • Ionic liquids are solid and liquid. The ionic liquid may be miscible with the electrolyte or may form a suspension with the electrolyte.
  • the cation constituting the ionic liquid is an imidazole cation, a quaternary ammonium cation, a quaternary phosphonium cation or a pyrrole cation.
  • the cation constituting the ionic liquid is an alkyl substituted imidazolium cation.
  • the alkyl group has a carbon number of from 1 to 10. More preferably, the carbon of the alkyl group The number of children is 1-5.
  • the ionic liquid is selected from the group consisting of 1-butyl-3-Methyl Imidazole Bisulfate (BMIMSO 4 H), 1-butyl-3-methyl 1-butyl-3-Methyl Imidazole Methyl sulfate (BMIMMS), 1-butyl-3-Methyl Imidazole Ethyl sulfate (referred to as 1-butyl-3-Methyl Imidazole Ethyl sulfate) BMIMES), 1-butyl-3-Methyl Imidazole Tetrafluoroborate (BMIMBF 4 ), 1-butyl-3-methylimidazolium hexafluorophosphate (1 -butyl-3-Methyl Imidazole Hexafluorophosphate (BMIMPF 6 ), 1-ethyl-3-Methyl Imidazole Ethyl sulfate (EMIMES), 1-ethyl- One or more of 1-ethyl- One or more
  • the ionic liquid is 1-butyl-3-methylimidazolium hydrogensulfate.
  • the mass fraction of the ionic liquid in the electrolyte affects the effect of the present invention.
  • the ionic liquid comprises from 0.1% to 50% by mass of the electrolyte.
  • the mass ratio of the ionic liquid to the electrolyte is in the range of 0.1 to 5%. More preferably, the mass ratio of the ionic liquid to the electrolyte is in the range of 0.5 to 1%. In a specific embodiment, the mass ratio of the ionic liquid to the electrolyte is 2%.
  • the electrolyte of the present invention increases the density of the electrolyte and lowers the vapor pressure by adding an ionic liquid, which greatly reduces the evaporation of water in the electrolyte. This allows the battery to improve cycle performance.
  • the electrolyte also has a lower melting point of the electrolyte, which improves the low temperature performance of the electrolyte.
  • the electrolyte also increases the ionic conductivity of the electrolyte by adding an ionic liquid.
  • the electrolyte of the present invention further comprises a ruthenium compound.
  • the cerium compound is cerium oxide.
  • the manner in which the additive is added to the electrolyte is not limited, and the solvent may be added together with the electrolyte; the solvent may be added before the electrolyte; or the solvent may be added after the electrolyte.
  • lithium ions and zinc ions are included in the electrolyte.
  • lithium ions are intercalated-extracted at the positive electrode, and zinc ions are deposited-dissolved at the negative electrode.
  • the electrolyte contains bromide ions and zinc ions.
  • bromide ions undergo an oxidation-reduction reaction at the positive electrode, and zinc ions are deposited-dissolved at the negative electrode.
  • both the first anion and the second anion are mesylate ions.
  • the concentration of the first metal ion is 0.5 to 15 mol/L.
  • the concentration of the anion in the electrolytic solution is from 0.5 to 12 mol/L.
  • the pH of the electrolyte is two.
  • the present invention also provides a battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte employs the above electrolyte.
  • the second metal ion can undergo a reversible reduction deposition-oxidation dissolution reaction on the negative electrode;
  • the positive electrode includes a positive electrode active material capable of reversibly extracting-embeding the first metal ion;
  • the first metal ion and the second metal ion are included, and during the charging and discharging process, the second metal ion can be reducedly deposited into a second metal at the negative electrode and the second metal can be reversibly oxidized and dissolved into the second metal ion, the first metal
  • the ions can be reversibly extracted and embedded in the positive electrode.
  • the negative electrode of the battery is capable of undergoing a reversible reduction deposition-oxidation dissolution reaction.
  • the second metal ion in the electrolyte can be reduced to the second metal on the negative electrode side and deposited on the negative electrode, and the second metal deposited on the negative electrode is reoxidized to the second metal ion into the electrolyte during discharge.
  • the second metal ion is manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion. More preferably, the second metal ion is a zinc ion.
  • the negative electrode material of the battery can be divided into the following four different forms according to the structure and the effect:
  • the negative electrode includes only the negative electrode current collector, and the negative electrode current collector serves only as a carrier for electron conduction and collection, and does not participate in the electrochemical reaction.
  • the anode current collector may also be selected from a metal containing a plating/coating having a high hydrogen evolution potential, thereby reducing the occurrence of a negative side reaction.
  • the plating/coating layer is selected from at least one of a simple substance, an alloy, or an oxide containing C, Sn, In, Ag, Pb, Co.
  • the thickness of the plating/coating ranges from 1 to 1000 nm.
  • tin, lead or silver is plated on the surface of the anode current collector of copper foil or graphite foil.
  • the negative electrode active material exists in the form of a sheet or a powder.
  • the metal powder is slurried, and then the slurry is coated on the negative electrode current collector to form a negative electrode.
  • the negative electrode conductive agent and the negative electrode binder are added as needed to improve the performance of the negative electrode.
  • the negative electrode is the porous negative electrode described in [Embodiment 1], and will not be described in detail herein.
  • the positive electrode and the separator described in the first embodiment are used for the positive electrode and the separator of the battery, and will not be described in detail here.
  • the electrolyte solution including the ionic liquid described above may also be combined with the porous negative electrode proposed in the first embodiment of the present invention to constitute a battery.
  • the invention provides a battery comprising a positive electrode, a negative electrode and an electrolyte
  • the positive electrode comprises a positive electrode material
  • the positive electrode material comprises a positive electrode binder, a positive electrode conductive agent and a positive electrode active material
  • the positive electrode active material comprises a positive electrode binder and can be reversibly desorbed - Embedding a first metal ion
  • the electrolyte comprises a solvent water and an electrolyte, the electrolyte is capable of at least ionizing the first metal ion and the second metal ion
  • the first metal ion is reversibly deintercalated-embedded in the positive electrode during charging and discharging
  • the second metal ion During the charging process, the anode is reduced to a second metal, and the second metal is oxidized and dissolved into a second metal ion during the discharging process.
  • the charging and discharging principle of the battery of the present invention is: when charging, the positive electrode active material desorbs the first metal ion, and the positive electrode active material is oxidized and emits electrons; the electron reaches the battery negative electrode through the external circuit, and the second metal ion in the electrolyte Electrons obtained on the negative electrode were reduced and deposited on the negative electrode. During discharge, the second metal deposited on the negative electrode is oxidized, and the lost electrons are converted into the second metal ions into the electrolyte; the electrons reach the positive electrode through the external circuit, the positive active material accepts the electrons to be reduced, and the first metal ions are embedded in the positive electrode active. In matter.
  • the positive electrode active material, the positive electrode current collector, the positive electrode conductive agent, and the separator are the positive electrode active material, the positive electrode current collector, the positive electrode conductive agent, and the separator which have been described in the first embodiment, and the negative electrode is used in [Embodiment 2].
  • the negative electrode and the electrolytic solution the electrolytic solutions described in [Embodiment 1] and [Embodiment 2] are not described in detail herein.
  • the positive electrode binder added to the positive electrode active material functions to adhere the positive electrode active material and the positive electrode conductive agent together and to be held on the current collector to enhance the electronic contact between the positive electrode active material and the positive electrode current collector.
  • the positive electrode binder includes at least one of an acrylonitrile multicomponent copolymer (LA133), polyacrylic acid (PAA), and hydroxypropylmethylcellulose (HPMC).
  • LA133 acrylonitrile multicomponent copolymer
  • PAA polyacrylic acid
  • HPMC hydroxypropylmethylcellulose
  • the battery provided by the invention is a water-based battery, and the working voltage range of the battery is generally 1.4-2.1V.
  • the positive electrode conductive agent is oxidized at a high voltage.
  • the gas is generated inside the battery, and the gas hinders the positive electrode from being wetted by the aqueous electrolyte, thereby improving the interface resistance between the positive electrode and the electrolyte.
  • the positive electrode binder provided in the second method can mainly improve the hydrophilicity of the positive electrode, reduce the interface resistance between the positive electrode and the aqueous electrolyte, and reduce the internal resistance of the battery.
  • the positive electrode binder accounts for 1% to 10% by mass of the positive electrode material. Such a setting not only ensures an effective combination of the positive electrode active material and the positive electrode conductive agent, but also does not affect the energy density of the battery.
  • the positive electrode binder comprises, in addition to at least one of LA133, PAA and HPMC, the positive electrode binder further comprises carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), carboxy.
  • CMC carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • Derivatives of styrene butadiene rubber include, but are not limited to, hydrophilically modified styrene butadiene rubber (PSBR).
  • the positive electrode binder comprises LA133 and CMC; in another embodiment, the positive electrode binder comprises LA133, CMC and SBR; in another embodiment, the positive electrode binder comprises LA133, CMC and PSBR .
  • the positive electrode binder includes, in addition to at least one of LA133, PAA, and HPMC, the positive electrode binder further includes an oxide, and the oxide includes titanium oxide, silicon oxide, and aluminum oxide. At least one.
  • the positive electrode binder includes at least one of LA133, PAA and HPMC
  • the positive electrode binder further includes other organic polymers or oxides, preferably, the weight of LA133 in the positive electrode binder The percentage is 10%-90%. More preferably, the weight percentage of LA133 in the positive electrode binder is 50%-75%, and the arrangement can significantly improve the self-discharge of the positive electrode and improve the floatation life of the battery.
  • LA133 is often used as a negative electrode binder for lithium ion batteries because of its strong bonding property, thereby suppressing the occurrence of powder drop during charging and discharging of the negative electrode.
  • LA133 is used as a positive electrode binder for water-based batteries, which mainly suppresses the loss of the positive electrode conductive agent, reduces self-discharge, and improves the battery float life.
  • the viscosity of the positive electrode slurry ranges from 4 ⁇ 10 4 to 6 ⁇ 10 4 mPa ⁇ s; in the preparation of hydroxypropylmethyl group
  • the viscosity of the positive electrode slurry ranges from 0.5 ⁇ 10 4 to 2 ⁇ 10 4 mPa ⁇ s.
  • the positive electrode binder comprises HPMC and SBR.
  • the positive electrode binder used in the battery of the invention improves the wettability of the positive electrode sheet, suppresses the oxygen bubbles generated inside the battery, hinders the positive electrode from being wetted by the electrolyte, reduces the interface impedance between the electrolyte and the positive electrode material, improves the floatation performance of the battery, and reduces the performance.
  • the battery is self-discharged.
  • the present invention also provides a battery pack comprising a plurality of the above-described batteries, in particular, a battery pack is produced by connecting two or more batteries in series, in parallel, or a combination thereof.
  • the capacity and voltage of the battery pack can be freely adjusted by series and/or parallel connection of the batteries.
  • a battery or a battery pack constructed in accordance with the present invention can be used as a power source for vehicles and transportation means such as trains, and as a fixed/installable power source such as an uninterruptible power source.
  • the positive electrode current collector is a graphite foil, and the positive electrode slurry is coated on the positive electrode current collector to form an active material layer, which is then subjected to tableting to prepare a positive electrode sheet.
  • the positive electrode sheet has a thickness of 0.4 mm, and the positive electrode active material has an areal density of 750 g/ m 2 .
  • negative electrode zinc active material zinc oxide and zinc, conductive agent acetylene black, additive cerium oxide, indium oxide, lead oxide and calcium hydroxide, binder PTFE and HPMC mixed, dispersed in deionized water, stirred uniformly to obtain negative electrode slurry
  • the negative electrode slurry was coated on a negative electrode current collector punched copper foil having a pore diameter of 0.8 mm and a thickness of 0.2 mm, and dried, rolled, and sheared to obtain a porous zinc negative electrode sheet.
  • the weight percentage of each component in the anode material is: zinc oxide 80%, zinc 9%, acetylene black 2%, cerium oxide 2%, indium oxide 1%, lead oxide 0.5%, calcium hydroxide 3%, PTFE 2%, HPMC 0.5%.
  • the porous zinc negative electrode sheet is externalized to reduce zinc oxide to zinc.
  • the porous zinc negative electrode sheet and the nickel positive electrode are placed in a 6 mol/L potassium hydroxide solution, and are charged at a constant voltage of 2.1 V and a constant current of 0.2 C. , charging until the charging capacity reaches 150% of the theoretical capacity of zinc oxide in the negative electrode, and washing the negative electrode to neutral with deionized water.
  • a certain amount of zinc sulfate and lithium sulfate were weighed and dissolved in water to prepare an electrolyte having a zinc sulfate concentration of 2 mol/L and a lithium sulfate concentration of 1 mol/L.
  • the electrolyte was dropped on the separator, and the positive electrode, the separator, and the negative electrode were laminated into a battery cell, and then placed in a casing to assemble a battery having a capacity of 250 mAh.
  • Example 1-2 the procedure for preparing the positive electrode was the same as in Example 1-1.
  • negative electrode zinc active material zinc, conductive agent acetylene black, additive indium oxide, lead oxide and calcium hydroxide, binder PTFE and HPMC mixed, dispersed in deionized water, stirred uniformly to obtain negative electrode slurry, negative electrode slurry
  • the film was coated on a negative electrode current collector punched copper foil having a pore diameter of 0.8 mm and a thickness of 0.2 mm, and dried, rolled, and sheared to obtain a porous zinc negative electrode sheet.
  • the weight percentage of each component in the negative electrode material is: zinc 89%, acetylene black 2%, cerium oxide 2%, indium oxide 1%, lead oxide 0.5%, calcium hydroxide 3%, PTFE 2%, HPMC 0.5%.
  • the porous zinc negative electrode sheet was not formed.
  • a certain amount of zinc sulfate and lithium sulfate were weighed and dissolved in water to prepare an electrolyte having a zinc sulfate concentration of 2 mol/L and a lithium sulfate concentration of 1 mol/L.
  • the electrolyte was dropped on the separator, and the positive electrode, the separator, and the negative electrode were laminated into a battery cell, and then placed in a casing to assemble a battery having a capacity of 250 mAh.
  • Comparative Example 1-1 the negative electrode of the battery was made of a 50 ⁇ m thick zinc foil negative electrode without being formed. The rest of the battery was constructed and prepared in the same manner as in Example 1-1.
  • the batteries in Examples 1-1 to 1-2 and Comparative Example 1-1 were subjected to constant current 100% DOD cycle charge and discharge at a rate of 0.2 C at 60 ° C, and the voltage range was 1.4-2.1 V.
  • Table 1 shows the number of cycles in which the first discharge capacity of the battery and the battery capacity dropped to 50% of the theoretical capacity.
  • the battery containing the porous zinc negative electrode obtained by externalization in Example 1-1 had the highest initial discharge capacity, and the second was a battery which was not externalized but also contained a porous zinc negative electrode in Example 1-2.
  • the battery with zinc foil as the negative electrode has the lowest initial discharge capacity; in addition, during the high temperature charge and discharge cycle, the discharge capacity of the battery in Example 1-1 decays slowly, and the battery discharge capacity drops to 50% of the theoretical capacity.
  • the battery cycle life in Example 1-1 was the longest, much larger than the cycle life of the battery in Comparative Example 1-1.
  • the batteries in the above Examples 1-1 to 1-2 and Comparative Example 1-1 were disassembled, and the dendrites on the surface of the negative electrode were observed.
  • the surface of the negative electrode of the battery had obvious dot dendrites, and the point dendrites in Example 1-1 need to be carefully observed to be found, and the point dendrites on the surface of the negative electrode in Example 1-2 were clearly compared.
  • the surface of the negative electrode in the ratio 1-1 is scarce.
  • the positive electrode current collector is a graphite foil, and the positive electrode slurry is coated on the positive electrode current collector to form an active material layer, which is then subjected to tableting to prepare a positive electrode sheet.
  • the positive electrode sheet has a thickness of 0.4 mm, and the positive electrode active material has an areal density of 750 g/ m 2 .
  • Preparation of the negative electrode zinc active material zinc oxide and zinc, binder polyvinyl alcohol PVA, polytetrafluoroethylene PTFE mixed, dispersed in deionized water, stirred uniformly to obtain a negative electrode slurry, the negative electrode slurry coated in a pore size of 0.8 A porous zinc negative electrode sheet was obtained by drying, rolling and shearing on a negative electrode current collector punched copper foil having a thickness of 0.2 mm and a thickness of 0.2 mm.
  • the porous zinc negative electrode sheet is externalized to reduce zinc oxide to zinc.
  • the porous zinc negative electrode sheet and the nickel positive electrode are placed in a 6 mol/L potassium hydroxide solution, and are charged at a constant voltage of 2.1 V and a constant current of 0.2 C. , charging until the charging capacity reaches 150% of the theoretical capacity of zinc oxide in the negative electrode, and washing the negative electrode to neutral with deionized water.
  • a certain amount of zinc sulfate and lithium sulfate were weighed and dissolved in water to prepare an electrolyte having a zinc sulfate concentration of 2 mol/L and a lithium sulfate concentration of 1 mol/L.
  • the electrolyte solution was dropped onto the AGM separator, and the positive electrode, the separator, and the negative electrode were laminated into a battery cell, and then placed in a casing to assemble a battery having a capacity of 250 mAh.
  • Comparative Example 1-2 the negative electrode of the battery was made of a 50 ⁇ m thick zinc foil negative electrode without being formed. The rest of the battery was constructed and prepared in the same manner as in Examples 1-3.
  • the batteries of Examples 1-3 and Comparative Examples 1-2 were subjected to a charge and discharge cycle test at a normal temperature of 0.2 V at a voltage ranging from 1.4 V to 2.1 V.
  • the batteries in Examples 1-3 showed that the discharge capacity was attenuated slowly and was able to run for up to 300 weeks, and the battery in Comparative Example 1-2 showed a sudden capacity drop problem at 137 weeks.
  • the batteries in the above Examples 1-3 and Comparative Examples 1-2 were disassembled, and dendritic conditions on the surface of the negative electrode were observed.
  • the surface of the negative electrode of the battery had obvious dot dendrites, and the point dendrites in Examples 1-3 need to be carefully observed to be found.
  • the battery containing the porous negative electrode solves the dendrite problem, and the cycle performance of the battery is improved, and the porous negative electrode obtained by externalization is used in the battery of the invention, and the dendrite problem of the negative electrode is remarkably improved, and the cycle life is improved. Multiplied.
  • the positive electrode current collector is a graphite foil, and the positive electrode slurry is coated on the positive electrode current collector to form an active material layer, which is then subjected to tableting to prepare a positive electrode sheet.
  • the positive electrode sheet has a thickness of 0.4 mm, and the positive electrode active material has an areal density of 750 g/ m 2 .
  • Preparation of the negative electrode zinc active material zinc, binder polyvinylidene fluoride PVDF, conductive agent activated carbon and graphite powder, dispersed in deionized water, stirred uniformly to obtain a negative electrode slurry, the negative electrode slurry is coated at a pore diameter of 0.8 mm, A porous zinc negative electrode sheet was obtained by drying, rolling and shearing on a negative electrode current collector punched copper foil having a thickness of 0.2 mm.
  • the weight percentage of each component in the negative electrode material is: zinc 79%, polyvinylidene fluoride PVDF7%, activated carbon 7%, and graphite powder 7%.
  • a certain amount of zinc sulfate and lithium sulfate were weighed and dissolved in water to prepare an electrolyte having a zinc sulfate concentration of 2 mol/L and a lithium sulfate concentration of 1 mol/L.
  • the electrolyte solution was dropped onto the AGM separator, and the positive electrode, the separator, and the negative electrode were laminated into a battery cell, and then placed in a casing to assemble a battery having a capacity of 250 mA.
  • Example 2-1 when preparing the negative electrode, the graphite powder is replaced by carbon nanotubes, and the weight percentage of each component in the negative electrode material is: zinc 79%, polyvinylidene fluoride PVDF 7%, activated carbon 7%, Carbon nanotubes 7%.
  • Example 2-1 when preparing the negative electrode, the graphite powder was replaced by Super-P, and the weight percentage of each component in the negative electrode material was: zinc 79%, polyvinylidene fluoride PVDF 7%, activated carbon 7%, Super-P 7%.
  • the conductive agent when preparing the negative electrode, only had activated carbon, and the weight percentage of each component in the negative electrode material was: zinc 79%, polyvinylidene fluoride PVDF 7%, and activated carbon 14%.
  • the cycle performance of the batteries in Examples 2-1 to 2-2 was superior to Comparative Example 2-1.
  • the battery in Embodiment 2-1 has a sudden capacity drop after running to 32 weeks; the battery in Embodiment 2-2 has a sudden capacity drop after running to 30 weeks;
  • the battery in Example 2-3 showed a sudden capacity drop after 20 weeks of operation, and the number of cycles was larger than that of the battery in Comparative Example 2-1.
  • the porous negative electrode battery using graphite and activated carbon in the negative electrode conductive agent of Example 2-1 has the best performance, and secondly, the negative electrode conductive agent in Example 2-2 is activated carbon-carbon nanotube. Porous negative battery.
  • the battery containing the porous negative electrode of the invention can significantly inhibit the dendrite problem of the negative electrode, can improve the cycle performance of the battery, and improve the electrochemical performance of the battery as a whole, so that the battery is more suitable for practical applications.
  • Example 3-1 The difference from Example 3-1 was that the electrolyte additive was an EMIMES ionic liquid, and the other portions were the same as those in Example 3-1.
  • Example 3-1 The difference from Example 3-1 was that the electrolyte additive was a BMIMDC ionic liquid, and the other portions were the same as those in Example 3-1.
  • Example 3-1 The difference from Example 3-1 was that the electrolyte additive was BMIMBF4 ionic liquid, and the other portions were the same as in Example 3-1.
  • the electrolyte additive was BMIMPF6 ionic liquid (solid), and the amount of BMIMPF6 was 1% by mass of the electrolyte.
  • the other parts are the same as those in the example 3-1.
  • the electrolyte additive is BMIMSO4H ionic liquid,
  • the other parts are the same as those in the example 3-1.
  • the electrolyte additive further included Bi2O3, and the amount of Bi2O3 added was 1% by mass of the electrolyte, and the other portions were the same as those in Example 3-1.
  • Example 3-1 The difference from Example 3-1 was that zinc sulfate was replaced with zinc methanesulfonate, lithium sulfate was replaced with lithium methanesulfonate, and the concentration of lithium methanesulfonate was changed to 3 mol/L.
  • Example 3-2 The difference from Example 3-2 was that zinc sulfate was replaced by zinc methanesulfonate, lithium sulfate was replaced by lithium methanesulfonate, and the concentration of lithium methanesulfonate was changed to 3 mol/L.
  • Example 3-3 The difference from Example 3-3 was that zinc sulfate was replaced with zinc methanesulfonate, lithium sulfate was replaced with lithium methanesulfonate, and the concentration of lithium methanesulfonate was changed to 3 mol/L.
  • Example 3-6 The difference from Example 3-6 was that zinc sulfate was replaced by zinc methanesulfonate, lithium sulfate was replaced by lithium methanesulfonate, and the concentration of lithium methanesulfonate was changed to 3 mol/L.
  • Example 3-1 The difference from Example 3-1 is that no ionic liquid is added to the electrolyte, and other parts are The same as Example 3-1.
  • Comparative Example 3-1 The difference from Comparative Example 3-1 was that zinc sulfate was replaced with zinc methanesulfonate, lithium sulfate was replaced with lithium methanesulfonate, and the concentration of lithium methanesulfonate was changed to 3 mol/L.
  • the working electrode and the counter electrode were made of zinc foil, the thickness of the zinc foil was 0.5 cm, the reference electrode was a saturated calomel electrode, and the electrolytes were respectively used in Examples 3-1 to 3-6, and Examples 3-10 to 3-15, Comparative Example 3-1, Comparative Example 3-2.
  • the corrosion current and the corrosion potential were calculated by the Tafel curve.
  • Examples 3-1 to 3-6 in which an ionic liquid was added had a smaller corrosion current.
  • Examples 3-5 to 3-6 have the minimum corrosion current.
  • Examples 3-10 to 3-15 in which an ionic liquid was added had a smaller corrosion current than Comparative Example 3-2 in which no ionic liquid was added.
  • Examples 3-13 and 3-15 have the smallest corrosion current. The smaller the corrosion current, the lower the corrosion of the electrolyte to the negative electrode, which helps to improve the performance of the battery.
  • the ionic liquid added to the electrolyte in the present invention is effective and can significantly reduce corrosion of the negative electrode.
  • Test conditions 5 ml of the electrolytes of Examples 3-1 to 3-6, Examples 3-10 to 3-15, Comparative Example 3-1, Comparative Example 3-2, and 0.5 g of zinc powder were mixed in one needle, respectively. In the barrel, close the end of the needle and shake it. The generated gas was tested by placing it at 60 ° C for 1 day.
  • the gas production amounts of Examples 3-1 to 3-6 in which the ionic liquid was added were reduced by about 6 to 62% as compared with the comparative example 3-1 in which the ionic liquid was not added.
  • the amount of gas produced in Examples 3-5 to which the ionic liquid was added was the most reduced, about 62%.
  • the ionic liquid added to the electrolyte in the present invention is effective, and the gas generation of the battery can be remarkably reduced.
  • Lithium manganate LMO, graphite conductive agent KS-6, and binder PVDF were mixed in NMP at a mass ratio of 86:7:7 to form a uniform positive electrode slurry.
  • the positive electrode slurry was coated on a positive electrode current collector conductive polyethylene material to form an active material layer, which was then tableted and cut to prepare a positive electrode sheet.
  • the negative electrode was a zinc foil sheet having a thickness of 0.05 mm, and a brass foil having a thickness of 0.02 mm was used as a negative electrode current collector.
  • the diaphragm is an AGM fiberglass membrane. The diaphragm and anode are the same size as the positive electrode.
  • the positive electrode sheet, the negative electrode sheet, and the separator were laminated and assembled into a battery cell, and placed in a casing, and then an electrolyte solution was injected and sealed to assemble a battery having a capacity of 250 mAh.
  • the electrolytic solution prepared in Example 3-3 was used as the electrolytic solution.
  • the electrolyte was prepared using the electrolytes prepared in Examples 3-5.
  • the electrolyte was prepared using the electrolytes prepared in Examples 3-6.
  • the electrolyte was prepared using the electrolytes prepared in Examples 3-7.
  • the electrolyte was prepared using the electrolytes prepared in Examples 3-9.
  • Examples 3-16 The difference from Examples 3-16 was that no ionic liquid was added to the electrolyte, and the other portions were assembled into batteries in the same manner as in Examples 3-16.
  • Example 3-22 The difference from Example 3-22 was that no ionic liquid was added to the electrolyte, and the other portions were assembled into a battery in the same manner as in Example 3-22.
  • Test conditions The batteries of Examples 3-16 to 3-21 were subjected to charge and discharge tests with a magnification of 0.2 C, a test temperature of 60 ° C, and a charge and discharge voltage range of 1.4-2.1 V.
  • the mass fraction of the ionic liquid added to the electrolyte was 0.2%, 0.5%, 1% as compared with Comparative Example 3-3 without the ionic liquid.
  • the battery has better cycle performance, and the battery shows the best cycle performance when the mass fraction of the ionic liquid added to the electrolyte is 1%.
  • Test conditions The batteries of Examples 3-18 were fully charged at 60 ° C for 1 day, the remaining capacity was tested, and capacity recovery was observed, and three tests were performed separately.
  • the batteries of Examples 3-21 were fully charged at 60 ° C for 7 days, the remaining capacity was tested, and capacity recovery was observed, and two tests were performed separately.
  • the capacity recovery rate refers to the percentage of the capacity and initial capacity obtained by performing the discharge test after the battery is fully charged after the second one or seven days of self-discharge.
  • the batteries of the battery examples 3 to 18 in which the ionic liquid was added exhibited better self-discharge capacity retention ratio and better capacity than the comparative example 3-3 in which the ionic liquid was not added.
  • the recovery rate, the batteries of Examples 3-21 showed substantially the same self-discharge capacity retention rate and a better capacity recovery rate.
  • Example 3-21 According to the data of Examples 3-21 in Tables 4 and 5, although the performance of Example 3-21 was not improved in the 1-day self-discharge performance test, compared with Comparative Example 3 in which the ionic liquid was not added, The 7-day self-discharge performance test showed better capacity retention and capacity recovery. Therefore, in the long run, the capacity retention rate and capacity recovery rate of the battery after the addition of the ionic liquid are higher than those of the battery without the ionic liquid.
  • the main problem to be solved is to suppress corrosion of the negative electrode, to ensure suppression of corrosion of the negative electrode, and to reduce dendrite of the negative electrode and Under the premise of gas production and greatly improving the cycle performance of the battery, it does not affect the self-discharge performance of the battery or even some improvement, which further illustrates the superiority of the technical solution of the present invention.
  • the addition of an ionic liquid to the electrolyte solution solves the problem of corrosion of the negative electrode, improves the gas production and cycle performance of the battery, and ensures that the self-discharge performance of the battery is not affected.
  • Test conditions The batteries of Examples 3-22 and Comparative Examples 3-4 were charged and discharged 3 times at 0.2 C, and the gas generated by floating at room temperature for 1 day was tested, and the float voltage was 2.0 V. The following data for this test is based on the gas pressure inside the battery.
  • the performance of the electrolyte can be improved, the corrosion, dendrites and gas production of the negative electrode are obviously suppressed, thereby improving the cycle performance, floatation performance and safety performance of the battery, and the overall improvement is improved.
  • the overall performance of the battery makes the battery more suitable for practical applications.
  • the binder acrylonitrile multicomponent copolymer (LA133) is sufficiently dissolved in water, and then the positive electrode active material lithium manganate LiMn 2 O 4 , the conductive agent SP-Li and the binder LA133 are at a mass ratio of 90:5:5.
  • the water is mixed and mixed to form a uniform positive electrode slurry, and the positive electrode slurry is coated on the positive electrode current collector conductive PE film and dried at 60 ° C for 12 hours, and the positive electrode active material has an areal density of 5-7 mg/cm 2 , which is then pressed.
  • the sheet was made into a positive electrode and was designated as S1.
  • Example 4-2 the binder polyacrylic acid (PAA) was first sufficiently dissolved in water, and then the positive electrode active material lithium manganate LiMn 2 O 4 , the conductive agent SP-Li and the binder PAA were mass ratio 90. : 5:5 mixed in water and mixed to form a uniform positive electrode slurry.
  • the positive electrode preparation process and the remaining composition were the same as those in Example 4-1, and the obtained positive electrode was designated as S2.
  • Example 4-3 the binder polyacrylic acid (PAA) was first dissolved in N-methylpyrrolidone (NMP), and then the positive electrode active material lithium manganate LiMn 2 O 4 , the conductive agent SP-Li and The binder PAA was mixed in water at a mass ratio of 90:5:5 and mixed to form a uniform positive electrode slurry.
  • NMP N-methylpyrrolidone
  • the positive electrode preparation process and the remaining composition were the same as those in Example 4-1, and the obtained positive electrode was designated as S3.
  • Example 4-4 the binder hydroxypropylmethylcellulose (HPMC) was first dissolved in water, and then the positive electrode active material lithium manganate LiMn 2 O 4 , the conductive agent SP-Li and the binder were used.
  • the HPMC is mixed in water at a mass ratio of 90:5:5 and mixed to form a uniform positive electrode slurry.
  • the positive electrode preparation process and the remaining composition were the same as those in Example 4-1, and the obtained positive electrode was designated as S4.
  • the binder was made of polyvinylidene fluoride (PVDF), the preparation process of the positive electrode and the rest of the composition were the same as those in Example 4-1, and the obtained positive electrode was designated as D1.
  • PVDF polyvinylidene fluoride
  • the hydrophilicity and the lyophilic electrolyte of the positive electrodes in Examples 4-1 to 4-4 and Comparative Example 4-1 were tested. Specifically, the contact angle was measured from the outer shape of the droplet formed on the positive electrode, and the photograph of the captured droplet shape was processed by the axisymmetric droplet shape analysis (ADSA) software to measure the advancing and receding contact angle of the droplet.
  • ADSA axisymmetric droplet shape analysis
  • the water droplets were placed on the positive electrode by a syringe to test the advancing contact angle and the receding contact angle of the water drop on the positive electrode.
  • the electrolytic solution was dropped on the positive electrode by a syringe.
  • the test results of the electrolyte are the same as those of the hydrophilic test.
  • the droplets of the electrolyte have the smallest forward and reverse contact angles measured on S1, followed by S2, S4 and S3, and advance on D1 containing the binder PVDF.
  • the receding contact angle is the largest.
  • the advancing contact angle of the electrolyte droplet on the positive electrode is significantly larger than the advancing contact angle of the water droplet on the positive electrode, indicating that the positive electrode is completely different in the electrolyte and is completely different in water.
  • the electrolyte and The wettability of S1 is the best, and the wettability with D1 is the worst.
  • the proper electrolyte penetration in the positive electrode coating is beneficial to the utilization of the positive electrode active material of the battery and the battery life.
  • the positive electrode in the same manner as in Example 4-1 was prepared.
  • the zinc sheet serves as a negative electrode.
  • the electrolytic solution was an aqueous solution containing 2 mol/L of lithium sulfate and 1 mol/L of zinc sulfate, and the pH of the electrolytic solution was adjusted to 4.3.
  • AGM acts as a diaphragm.
  • Example 4-2 The positive electrode of Example 4-2 was prepared, and the remaining battery preparation methods and compositions were the same as those of Examples 4-5.
  • the batteries in Examples 4-6 are designated as B2.
  • Example 4-3 The positive electrode of Example 4-3 was prepared, and the remaining battery preparation methods and compositions were the same as those of Examples 4-5.
  • the batteries of Examples 4-7 are designated as B3.
  • Example 4-4 The positive electrode of Example 4-4 was prepared, and the remaining battery preparation methods and compositions were the same as those of Examples 4-5.
  • the batteries of Examples 4-8 are designated as B4.
  • the positive electrode in the same Comparative Example 4-1 was prepared, and the remaining battery preparation method and composition were the same as those in Examples 4-5.
  • the battery in Comparative Example 4-2 was designated as D2.
  • the self-discharge and floatation properties of the battery were tested at room temperature and high temperature (60 ° C). Specifically, the batteries B1-B4 and D2 are charged and discharged three times at a rate of 0.2 C and a voltage range of 1.4 V-2.1 V, and the discharge capacity of the battery is tested before the capacity Q, and then the battery is charged to 2.1 V, and the battery is charged at 2.1 V. Float charge for 24 hours, test the battery's float charge flow; after floating charge for 24 hours, stop charging the battery, leave the battery for 72 hours, measure the voltage drop of the battery when the circuit is open, and after the battery is left for 72 hours, the battery is discharged at 0.2C. after the discharge specific capacity Q, the battery capacity retention ratio is defined equal to (the Q / before Q) ⁇ 100%.
  • the film was coated on a cathode current collector graphite foil, and dried at 60 ° C, and then subjected to tableting, and cut into an 8 ⁇ 10 cm size to prepare an anode surface active material having an areal density of 750 g/m 2 .
  • the negative electrode included two sheets of a 20 ⁇ m thick negative electrode active material zinc foil and one 20 ⁇ m thick negative electrode current collector brass foil, and the brass foil was placed between two zinc foils.
  • the electrolytic solution was a mixed aqueous solution of 2 mol/L of ZnSO 4 and 1 mol/L of Li 2 SO 4 to adjust the pH of the electrolytic solution to 5.
  • the separator was an AGM glass fiber, and antimony trioxide was added to the separator. Specifically, it was added to the side of the separator facing the negative electrode, and the amount of antimony trioxide added was 0.2 g/Ah.
  • the diaphragm and anode are the same size as the positive electrode.
  • 5 positive electrodes and 6 negative electrodes are staggered, and the positive and negative electrodes are separated by a diaphragm.
  • the theoretical capacity is about 5Ah, after the battery is assembled, the electrolyte is injected to saturation.
  • the remaining composition and preparation method of the battery were the same as in Examples 4-9.
  • the remaining composition and preparation method of the battery were the same as those in Examples 4-10.
  • the remaining composition and preparation method of the battery were the same as those in Examples 4-10.
  • the batteries of Examples 4-9-4-11 and Comparative Example 4-3 were subjected to charge and discharge cycles at a voltage of 1.4-2.1 V at a rate of 0.2 C at room temperature, and the battery capacity was calibrated. The battery was then floated at 1.90 V for 168 h (one week) at 60 ° C, and then discharged to 1.4 V at 0.2 C. Test the discharge capacity of the battery. The battery's floating capacity is reduced by reducing the discharge capacity of the battery to 50%.
  • the high-temperature accelerated float life test is a normal charge life of four months at a room temperature of 60 ° C for one week.
  • the high-temperature floatation life of the battery in Comparative Example 4-3 was 9 to 10 weeks, and the high-temperature floatation life of the battery in Examples 4-9 was 20% higher than that in the Comparative Example 4-3, and converted to normal temperature, Example 4
  • the battery life of the -9 battery has increased by 3-8 months.
  • the high temperature float life of the batteries in Examples 4-10 was 10% higher than that of the batteries in Comparative Example 4-3, and the high temperature float life of the batteries in Examples 4-11 was comparable to those of Examples 4-9. This result indicates that the positive electrode binders LA133 and CMC can significantly improve the battery floatation performance with respect to the binders SBR and CMC.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une batterie qui comprend une électrode positive, une électrode négative et un électrolyte aqueux ; l'électrode positive comprend une substance active d'électrode positive et un collecteur de courant d'électrode positive ; l'électrolyte aqueux comprend des premiers ions métalliques et/ou des seconds ions métalliques, les premiers ions métalliques sont aptes à être retirés de manière réversible de l'électrode positive ou intégrés dans celle-ci au cours d'un processus de charge et de décharge, les seconds ions métalliques sont réduits et déposés pour être un second métal au niveau de l'électrode négative pendant un processus de charge et le second métal est oxydé et dissous pour être les seconds ions métalliques dans un processus de décharge ; l'électrode négative comprend une substance d'électrode négative avec une structure poreuse et la substance d'électrode négative comprend une substance active de zinc et un agent d'adhérence d'électrode négative. La présente invention peut améliorer efficacement le problème des cristaux dendritiques au niveau d'une électrode négative d'une batterie, augmenter la durée de vie des batteries et améliorer les performances électrochimiques et les performances de sécurité des batteries.
PCT/CN2016/093598 2015-08-05 2016-08-05 Batterie, ensemble batterie et source d'alimentation non interruptible WO2017020860A1 (fr)

Applications Claiming Priority (6)

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CN201510474584.0A CN106450509A (zh) 2015-08-05 2015-08-05 电解液和电池
CN201510474584.0 2015-08-05
CN201510608168.5 2015-09-22
CN201510608168 2015-09-22
CN201510736618.9A CN106654274A (zh) 2015-11-03 2015-11-03 电池、电池组以及不间断电源
CN201510736618.9 2015-11-03

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CN111146408A (zh) * 2020-02-11 2020-05-12 河南创力新能源科技股份有限公司 一种铁镍电池负极的制备方法
CN111987934A (zh) * 2020-08-14 2020-11-24 河海大学 一种悬臂梁振动发电装置
CN112952212A (zh) * 2021-03-09 2021-06-11 中国科学技术大学 水系二氧化锰-金属二次电池
CN113140807A (zh) * 2021-04-21 2021-07-20 浙江大学 一种具有不燃性的水系电池
CN113299987A (zh) * 2021-05-25 2021-08-24 哈尔滨工业大学 一种锌离子电池固态聚合物电解质的制备方法
CN113346041A (zh) * 2021-05-19 2021-09-03 北京化工大学 一种利用正极材料作界面层构筑柔性金属负极的方法
CN113678218A (zh) * 2018-01-17 2021-11-19 黄潮 水系混合超级电容
CN113972376A (zh) * 2021-10-21 2022-01-25 中国石油天然气股份有限公司 一种三维金属骨架支撑多孔锌负极材料及其制备方法与应用
US20220045368A1 (en) * 2020-08-05 2022-02-10 Nano And Advanced Materials Institute Limited Rechargeable battery with aqueous-based electrolyte
CN114204137A (zh) * 2021-10-29 2022-03-18 华南协同创新研究院 一种有机镍离子电池电解液及有机镍离子电池
CN114597479A (zh) * 2021-06-26 2022-06-07 宁德时代新能源科技股份有限公司 平板式钠金属电池、电化学装置
CN114823158A (zh) * 2022-05-19 2022-07-29 一汽解放汽车有限公司 一种锌离子电容器及其制备方法与蓄电池
CN114927772A (zh) * 2022-06-28 2022-08-19 华中科技大学 一种电解液的添加剂及其应用、电解液和水系锌离子电池
CN114976299A (zh) * 2022-07-12 2022-08-30 中南大学 水系锌离子电池用湿砂电解液及其制备方法、水系锌离子电池
CN115403771A (zh) * 2022-09-06 2022-11-29 桂林理工大学 一种基于共轭羰基的聚酰亚胺的制备方法及其在铁离子电池负极材料方面的应用
CN115632132A (zh) * 2022-10-25 2023-01-20 辽宁金谷炭材料股份有限公司 一种铁铬液流电池的复合电极制备方法

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CN113678218A (zh) * 2018-01-17 2021-11-19 黄潮 水系混合超级电容
CN111146408B (zh) * 2020-02-11 2022-11-29 河南创力新能源科技股份有限公司 一种铁镍电池负极的制备方法
CN111146408A (zh) * 2020-02-11 2020-05-12 河南创力新能源科技股份有限公司 一种铁镍电池负极的制备方法
US20220045368A1 (en) * 2020-08-05 2022-02-10 Nano And Advanced Materials Institute Limited Rechargeable battery with aqueous-based electrolyte
CN111987934B (zh) * 2020-08-14 2024-04-02 河海大学 一种悬臂梁振动发电装置
CN111987934A (zh) * 2020-08-14 2020-11-24 河海大学 一种悬臂梁振动发电装置
CN112952212A (zh) * 2021-03-09 2021-06-11 中国科学技术大学 水系二氧化锰-金属二次电池
CN113140807A (zh) * 2021-04-21 2021-07-20 浙江大学 一种具有不燃性的水系电池
CN113140807B (zh) * 2021-04-21 2022-08-05 浙江大学 一种具有不燃性的水系电池
CN113346041A (zh) * 2021-05-19 2021-09-03 北京化工大学 一种利用正极材料作界面层构筑柔性金属负极的方法
CN113346041B (zh) * 2021-05-19 2022-07-12 北京化工大学 一种利用正极材料作界面层构筑柔性金属负极的方法
CN113299987A (zh) * 2021-05-25 2021-08-24 哈尔滨工业大学 一种锌离子电池固态聚合物电解质的制备方法
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CN114597479A (zh) * 2021-06-26 2022-06-07 宁德时代新能源科技股份有限公司 平板式钠金属电池、电化学装置
CN114597479B (zh) * 2021-06-26 2024-02-20 宁德时代新能源科技股份有限公司 平板式钠金属电池、电化学装置
CN113972376A (zh) * 2021-10-21 2022-01-25 中国石油天然气股份有限公司 一种三维金属骨架支撑多孔锌负极材料及其制备方法与应用
CN114204137B (zh) * 2021-10-29 2023-10-31 华南协同创新研究院 一种有机镍离子电池电解液及有机镍离子电池
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