CN103682476B - Battery - Google Patents

Abstract

The invention discloses a battery, which comprises a shell, and a positive electrode, a negative electrode, aqueous electrolyte and a diaphragm which are arranged in the shell, wherein the positive electrode comprises a composite current collector and a positive electrode active substance; the battery comprises n pairs of the positive electrodes and the negative electrodes, wherein n is larger than or equal to 2, two adjacent positive electrodes share the negative electrode positioned between the two positive electrodes, two adjacent negative electrodes share the positive electrode positioned between the two negative electrodes, and the positive electrodes and the negative electrodes are alternately arranged in the shell in a stacked mode. The battery provided by the invention has good cycle performance and higher energy, and is expected to be widely applied in the fields of large-scale energy storage, power grid peak regulation and the like.

Description

Battery

technical field

The invention belongs to the field of electrochemical energy storage, and in particular relates to a battery.

Background technique

The widespread use of new energy by human beings has led to the rapid expansion of the secondary battery market. In the current new energy system, the requirements for secondary batteries are ubiquitous. Whether it is electric vehicles, wind energy, solar grid connection or grid peak shaving, there is an urgent need for a cheap, reliable, safe and long-life secondary battery. The secondary batteries currently developed are mainly concentrated in lithium-ion batteries, high-temperature sodium-sulfur batteries, sodium-nickel-chloride batteries and vanadium flow batteries. These batteries have their own advantages, such as long life and high energy density of lithium-ion batteries and high-temperature sodium-sulfur batteries, and vanadium redox flow batteries have theoretically unlimited life. But no matter what kind of battery, it is impossible to meet the requirements of cheapness, reliability, safety and long life at the same time. Traditional lithium-ion batteries are too expensive and have potential safety hazards; high-temperature sodium-sulfur batteries have high technical thresholds and are expensive; many technical bottlenecks of vanadium redox flow batteries have not yet been broken through.

For this reason, many researchers are committed to the research of aqueous lithium-ion batteries, hoping to greatly reduce the cost of lithium-ion batteries and improve safety, and have proposed some LiMn ₂ O ₄ as the positive electrode, vanadium oxides such as LiV ₃ O ₈ and so on are batteries with negative electrodes and water as electrolyte, but the poor stability of charging and discharging of such negative electrodes in water and the certain toxicity of vanadium limit the development of such batteries. So far, the structures of the proposed aqueous lithium-ion secondary batteries have not been able to get rid of the structure based on the lithium ion extraction-intercalation principle, such as the reported VO ₂ /LiMn ₂ O ₄ , LiV ₃ O ₈ /LiNi _0.81 Co _0.19 O ₂ , TiP ₂ O ₇ /LiMn ₂ O ₄ , LiTi ₂ (PO ₄ ) ₃ /LiMn ₂ O ₄ , LiV ₃ O ₈ /LiCoO ₂ , etc.

Contents of the invention

The invention aims to provide a battery with simple structure, low cost, safety and reliability and long cycle life.

The invention provides a battery, including a casing, a positive electrode, two negative electrodes, an aqueous electrolyte and a diaphragm arranged in the casing, the positive electrode includes a composite current collector and a 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 composite current collector has a first surface and a second surface oppositely arranged, and the positive electrode active material is arranged on the first surface and the second surface Above, the positive electrode active material can reversibly extract-insert ions; the negative electrode is selected from metals, alloys or carbon-based materials; the aqueous electrolyte includes an electrolyte, and the electrolyte can at least ionize active ions, and the active ions are When charging, it is reduced and deposited on the negative electrode to form a negative active material, and the negative active material is oxidized and dissolved in the aqueous electrolyte during discharge; the diaphragm maintains the aqueous electrolyte; the positive and negative layers are stacked Distributed in the casing, the positive electrode is placed between the two negative electrodes, the two negative electrodes share the positive electrode, and the separator is located between the positive electrode and the negative electrode.

The present invention also provides a battery, including a casing, two positive electrodes, a negative electrode, an aqueous electrolyte and a diaphragm arranged in the casing, the positive electrode includes a composite current collector and a positive electrode active material, and the composite current collector Comprising a positive current collector and a conductive film coated on the positive current collector, the composite current collector has a first face and a second face opposite to each other, the first face is opposite to the negative electrode, and at least the second face The positive electrode active material is provided on one side, and the positive electrode active material can reversibly extract-intercalate ions; the negative electrode is selected from metal, alloy or carbon-based materials; the aqueous electrolyte includes an electrolyte, and the electrolyte can at least ionize The active ions are released, and the active ions are reduced and deposited on the negative electrode during charging to form negative active materials, and the negative active materials are oxidized and dissolved in the aqueous electrolyte during discharge; liquid; the positive electrode and the negative electrode are stacked and arranged in the casing, the negative electrode is placed between the two positive electrodes, the two positive electrodes share the negative electrode, and the separator is located between the positive electrode and the negative electrode between.

The present invention also provides a battery, including a casing, a positive electrode, a negative electrode, an aqueous electrolyte and a diaphragm arranged in the casing, the positive electrode includes a composite current collector and a positive electrode active material, and the composite current collector includes a positive electrode A current collector and a conductive film coated on the positive electrode current collector, the composite current collector has two opposite sides, wherein at least one side of the composite current collector opposite to the negative electrode is provided with a positive electrode active material, so The positive electrode active material can reversibly extract-intercalate ions; the battery includes n pairs of the positive electrode and the negative electrode, n≥2, the adjacent two positive electrodes share the negative electrode between the two positive electrodes, and the adjacent two negative electrodes share the A positive electrode positioned between two negative electrodes; the negative electrode is selected from metals, alloys, or carbon-based materials; the aqueous electrolyte includes an electrolyte capable of at least ionizing active ions that are reductively deposited during charging The negative active material is formed on the negative electrode, and the negative active material is oxidized and dissolved in the aqueous electrolyte during discharge; the diaphragm keeps the aqueous electrolyte; the positive and negative electrodes are alternately stacked and arranged on the In the casing, the separator is located between the positive and negative electrodes.

The battery provided by the invention can well solve the problem of self-discharge. The battery is safe in operation, simple in manufacturing method, excellent in cycle performance and long in life. At the same time, batteries with different output discharge capacities can be set according to usage requirements, and the battery has a wide range of uses.

Preferably, the housing is square.

Preferably, the positive electrode, the separator and the negative electrode are formed into a flat plate.

Preferably, the positive electrode, the separator and the negative electrode are wound and formed.

Preferably, the casing is cylindrical, and the positive electrode, the separator, the negative electrode and the casing are coaxially arranged.

Preferably, the positive electrode, the separator and the negative electrode are wound to form a cylindrical shape and arranged in the casing.

Preferably, the material of the conductive film includes polymer and conductive filler.

Preferably, the polymer is selected from polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, polycarbonate, polymethyl methacrylate, polyoxymethylene, polyphenylene ether, polysulfone , at least one of polyethersulfone, styrene-butadiene rubber or fluororesin.

Preferably, the conductive filler is selected from conductive polymers, carbon-based materials or metal oxides.

Preferably, the material of the conductive film is selected from conductive polymers.

Preferably, the housing is configured as an aluminum-plastic film.

Preferably, a liquid replenishment port is provided on the housing, and the liquid replenishment port is used to replenish the aqueous electrolyte.

Preferably, the battery further includes a safety valve for controlling the pressure in the casing.

Preferably, the positive active material has a spinel structure, a layered structure or an olivine structure.

Preferably, the material of the positive electrode current collector is selected from one of glassy carbon, graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or one of the above metals with passivation treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or passivated One of the above alloys treated.

Preferably, the material of the negative electrode is selected from at least one of the metals Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al, or the metals that have been passivated, or at least one of the alloys containing the above metals One, or at least one of graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or tinned copper, or brass.

Preferably, the active ions include metal ions, and the metal is selected from at least one of Zn, Fe, Cr, Cu, Mn, Ni, and Sn.

Preferably, the active ions exist in the aqueous electrolyte in the form of at least one of hydrochloride, sulfate, acetate, nitrate or formate.

The present invention also provides a battery, including a casing, a positive lead-out electrode, at least one bipolar electrode, a negative lead-out electrode and an aqueous electrolyte disposed in the casing, the positive lead-out electrode includes a positive current collector and a set The positive electrode active material on one side of the positive electrode current collector, the positive electrode active material can reversibly extract-intercalate ions; the bipolar electrode is arranged between the positive extraction electrode and the negative extraction electrode, and the bipolar electrode Comprising a bipolar current collector and the positive electrode active material, the bipolar current collector has a first surface and a second surface oppositely arranged, the positive electrode active material is arranged on the first surface of the bipolar current collector above; the aqueous electrolyte includes an electrolyte, the electrolyte can at least ionize active ions, and the active ions are reduced and deposited on the second surface of the bipolar current collector to form a negative electrode active material during charging, and the negative electrode The active material is oxidized and dissolved in the aqueous electrolyte during discharge; the negative extraction electrode is selected from metal, alloy or carbon-based materials; the aqueous electrolyte is arranged between the positive extraction electrode and the negative extraction electrode; The positive extraction electrode, the bipolar electrode and the negative extraction electrode are stacked and arranged in the casing.

The battery provided by the invention has the advantages of safe operation, simple manufacturing method, excellent cycle performance and long service life. At the same time, batteries with different output voltages can be provided according to usage requirements, and the batteries have wide applications.

Preferably, the housing is set in a square shape.

Preferably, the positive lead-out electrode, the bipolar electrode and the negative lead-out electrode are formed into a flat plate shape.

Preferably, the battery further includes a separator, and the separator holds the aqueous electrolyte.

Preferably, the positive electrode collector is coated with a conductive film.

Preferably, the outer peripheral portion of the bipolar current collector is provided with a sealing portion for sealing the aqueous electrolyte.

Preferably, the material of the bipolar current collector includes conductive plastic, stainless steel or passivated stainless steel.

Preferably, the material of the conductive plastic is selected from conductive polymers.

Preferably, the material of the conductive plastic includes a polymer and a conductive agent.

Preferably, the housing is configured as an aluminum-plastic film.

Preferably, a liquid replenishment port is provided on the housing, and the liquid replenishment port is used to replenish the electrolyte.

Preferably, the battery further includes a safety valve for controlling the pressure in the casing.

Preferably, the positive active material has a spinel structure, a layered structure or an olivine structure.

Preferably, the material of the positive electrode current collector is selected from one of glassy carbon, graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or one of the above metals with passivation treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or passivated One of the above alloys treated.

Preferably, the material of the negative lead-out electrode is selected from at least one of the metals Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al, or the metals that have undergone passivation treatment, or an alloy containing the above metals At least one of, or at least one of graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or tinned copper, or brass.

Preferably, the active ions include metal ions, and the metal is selected from at least one of Zn, Fe, Cr, Cu, Mn, Ni, and Sn.

Preferably, the active ions exist in the aqueous electrolyte in the form of at least one of hydrochloride, sulfate, acetate, nitrate or formate.

The present invention also provides a battery, including a casing, a positive electrode, a diaphragm, a negative electrode and an aqueous electrolyte disposed in the casing, the positive electrode includes a positive electrode current collector and a positive electrode active material participating in an electrochemical reaction, the positive electrode The active material includes a compound capable of reversibly extracting and intercalating ions; the negative electrode is selected from metals, alloys or carbon-based materials; the aqueous electrolyte includes an electrolyte, and the electrolyte can at least ionize active ions, and the active ions are charged when charged It is reduced and deposited on the negative electrode to form a negative active material, and the negative active material is oxidized and dissolved in the aqueous electrolyte during discharge; the positive electrode, the separator and the negative electrode are stacked in the casing , the separator is located between the positive electrode and the negative electrode.

The battery provided by the invention has simple structure, safe operation, low production cost and considerable service life, and is suitable as an energy storage system in the field of large-scale energy storage and a substitute for lead-acid batteries.

Preferably, the housing is square.

Preferably, the positive electrode, the separator and the negative electrode are formed into a flat plate.

Preferably, the positive electrode, the separator and the negative electrode are wound and formed.

Preferably, the housing is made of aluminum-plastic film.

Preferably, a liquid replenishment port is provided on the housing, and the liquid replenishment port is used to replenish the aqueous electrolyte.

Preferably, the battery further includes a safety valve for controlling the pressure in the casing.

Preferably, the positive active material has a spinel structure, a layered structure or an olivine structure.

Preferably, the material of the positive electrode current collector is selected from one of glassy carbon, graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or one of the above metals with passivation treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or passivated One of the above alloys treated.

Preferably, the material of the negative electrode is selected from at least one of the metals Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al, or the metals that have been passivated, or at least one of the alloys containing the above metals One, or at least one of graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or tinned copper, or brass.

Preferably, the active ions include metal ions, and the metal is selected from at least one of Zn, Fe, Cr, Cu, Mn, Ni, and Sn.

Preferably, the active ions exist in the aqueous electrolyte in the form of at least one of hydrochloride, sulfate, acetate, nitrate or formate.

The present invention also provides a battery, including a casing, a positive electrode, a diaphragm, a negative electrode and an aqueous electrolyte disposed in the casing, the positive electrode includes a positive electrode current collector and a positive electrode active material participating in an electrochemical reaction, and the positive electrode active material Comprising a compound capable of reversibly de-intercalating ions; the negative electrode is selected from metals, alloys, or carbon-based materials; the aqueous electrolyte includes an electrolyte capable of at least ionizing active ions that are reduced upon charging Deposited on the negative electrode to form a negative electrode active material, the negative electrode active material is oxidized and dissolved in the aqueous electrolyte during discharge; the positive electrode, the separator and the negative electrode are stacked and arranged in the casing, The separator is located between the positive electrode and the negative electrode.

The battery provided by the invention has high energy density, safety and non-toxicity, environmental protection, easy recycling and low cost. As a new generation of green energy, the battery in the invention is very suitable as an energy storage system in the field of large-scale energy storage and a lead-acid battery replacement of.

Preferably, the casing is configured in a cylindrical shape, and the positive electrode, the separator, the negative electrode and the casing are coaxially arranged.

Preferably, the positive electrode, the separator and the negative electrode are wound and arranged in the casing in a cylindrical shape.

Preferably, both the negative electrode and the separator are cylindrical, the positive current collector is cylindrical, and the positive active material is disposed between the separator and the positive current collector.

Preferably, the battery further includes a fixing ring, and the fixing ring fixes the positive electrode current collector, the separator, the negative electrode and the casing; the material of the fixing ring is polyvinyl chloride, and the fixing ring There are two, respectively arranged at the two ends of the housing.

Preferably, the fixing ring includes an upper ring and a lower ring, the upper ring and the lower ring are integrally formed, the upper ring fixes the positive current collector and the separator, and the lower ring fixes the separator with the negative pole.

Preferably, the outer diameter of the upper ring is the same as the inner diameter of the negative electrode, the inner diameter of the upper ring is the same as the diameter of the positive current collector; the outer diameter of the lower ring is the same as the inner diameter of the diaphragm, so The inner diameter of the lower ring is the same as the diameter of the positive current collector.

Preferably, the housing is made of aluminum-plastic film.

Preferably, a liquid replenishment port is provided on the housing, and the liquid replenishment port is used to replenish the aqueous electrolyte.

Preferably, the battery further includes a safety valve for controlling the pressure in the casing.

Preferably, the positive active material has a spinel structure, a layered structure or an olivine structure.

Preferably, the material of the positive electrode current collector is selected from one of glassy carbon, graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or one of the above metals with passivation treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or passivated One of the above alloys treated.

Preferably, the material of the negative electrode is selected from at least one of the metals Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al, or the metals that have been passivated, or at least one of the alloys containing the above metals One, or at least one of graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or tinned copper, or brass.

Preferably, the active ions include metal ions, and the metal is selected from at least one of Zn, Fe, Cr, Cu, Mn, Ni, and Sn.

Preferably, the active ions exist in the aqueous electrolyte in the form of at least one of hydrochloride, sulfate, acetate, nitrate or formate.

Description of drawings

FIG. 1 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 1;

Fig. 2 is the structural representation of composite current collector in Fig. 1;

Fig. 3 is a schematic structural view of the cell in Fig. 1, wherein the battery unit is schematically shown;

4 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 2;

5 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 2, wherein positive active materials are provided on both sides of the composite current collector opposite to each other;

6 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 3, wherein the battery includes two pairs of positive and negative electrodes;

7 is a schematic cross-sectional view of the battery provided in the third embodiment, wherein positive active materials are provided on both sides of the outermost positive electrode composite current collector;

Fig. 8 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 3, wherein the logarithm of the positive electrode and the negative electrode is greater than 2;

9 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 4;

Fig. 10 is a schematic structural view of the bipolar electrode in Fig. 9;

Fig. 11 is a schematic diagram of the battery structure in Fig. 9, wherein the battery cells are schematically shown;

Fig. 12 is a schematic diagram of the charging principle of the battery provided in Embodiment 4;

13 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 5;

Fig. 14 is a schematic structural diagram of the battery in Fig. 13, wherein the battery unit is schematically shown;

Fig. 15 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 6;

16 is a schematic cross-sectional view of the overall structure of the battery provided in Embodiment 7;

Fig. 17 is a schematic structural diagram of a battery provided in Embodiment 8;

Fig. 18 is a schematic structural view of the battery provided in the eighth embodiment, the separator is folded in a Z shape;

Fig. 19 is a schematic diagram of the unfolded state of the battery in Fig. 18;

Fig. 20 is a schematic structural view of the battery provided in the eighth embodiment, wherein the battery is wound and formed;

Fig. 21 is a schematic disassembly diagram of the structure of the battery in Embodiment 9;

Fig. 22 is a schematic structural view of the fixing ring in the middle battery in Fig. 21;

FIG. 23 is a charge-discharge cycle performance diagram of the battery provided in Example 1.

in:

1. Battery 2, 72. Positive pole 4, 74, 160. Negative pole

6, 78. Aqueous electrolyte 8. Composite current collector 10, 82. Positive electrode active material

12, 80, 152. Positive electrode collector 14. Conductive film 16, 76, 156. Diaphragm

20. Battery unit 22, 70. Housing 24, 84. Cover

26, 86. Sealing cap 28, 88. Safety valve 81. First side

82. Second side 30, 40, 50. Battery 100. Battery

52. Bipolar electrode 54. Positive lead-out electrode 56. Bipolar current collector

61. First side 62. Second side 58. Negative extraction electrode

60. Sealing part 64, 68. Battery unit 90. Plane

110, 120, 130. Battery 140, 150. Battery 92. Arc

94. Positive Winding Termination 96. Negative Winding Termination 154. Retaining Ring

158. Positive active material 162. Upper ring 164. Lower ring

detailed description

The battery provided by the invention has high energy density and stable cycle performance, and has considerable application prospects in portable electronic products such as mobile phones and notebook computers, electric vehicles, electric tools and the like.

[Battery with internal parallel structure]

A battery having an internal parallel structure. The battery with an internal parallel structure will be described below with reference to the drawings and specific embodiments.

Implementation Mode 1

Please refer to FIG. 1 , a battery 1 includes a casing 22 , a positive electrode 2 disposed in the casing 22 , two negative electrodes 4 , an aqueous electrolyte 6 and a separator 16 . The positive electrode 2 and the negative electrode 4 are stacked and arranged in the casing 22, the positive electrode 2 is placed between the two negative electrodes 4, the two negative electrodes 4 share the positive electrode 2, the diaphragm 16 is located between the positive electrode 2 and the negative electrode 4, and the diaphragm 16 maintains the aqueous electrolyte 6.

The housing 22 can be made of metal, plastic or a composite film of metal and plastic, such as steel, aluminum, acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), nylon or aluminum-plastic film and the like. Preferably, the casing 22 is made of an aluminum plastic film, so that the casing is thinner, reducing the weight of the battery and increasing the space inside the battery. The aluminum-plastic film includes a layer of aluminum sheet and a plastic sheet arranged on one side of the aluminum sheet. Preferably, the aluminum-plastic film includes a layer of aluminum sheet and a first layer of plastic sheet and a second layer of plastic sheet arranged on both sides of the aluminum sheet.

The housing 22 may be configured as a square shape.

Specifically, the negative electrode 4 , the separator 16 , the positive electrode 2 , the separator 16 and the negative electrode 4 are stacked and arranged to form a flat plate, and placed in the casing 22 , as shown in FIG. 1 . Therefore, the battery 1 can be designed as a square battery, such as a rectangular parallelepiped or a cube. The battery has the advantages of simple structure, convenient manufacture and low cost.

In addition, the negative electrode 4 , the separator 16 , the positive electrode 2 , the separator 16 and the negative electrode 4 are stacked in order to form a flat plate, and then wound to form a flat battery cell. Preferably, the positive electrode 2, the separator 16 and the negative electrode 4 are all arranged in a strip shape. According to the design of the battery, it needs to be wound into different numbers of turns.

The casing can also be set in a cylindrical shape (not shown).

Specifically, the negative electrode 4, the separator 16, the positive electrode 2, the separator 16 and the negative electrode 4 are stacked and arranged to form a flat plate, and then a cylindrical cell is formed by winding and placed in the casing. The positive electrode 2, the separator 16, the negative electrode 4 and the The shells are arranged coaxially. Therefore, the battery can be designed as a cylindrical battery, and the battery has a simple structure and is convenient to manufacture.

Specifically in the first embodiment, the battery further includes a cover 24 connected to the casing 22 , the positive electrode 2 extends out of the cover 24 , and a sealing cap 26 is provided at the end of the positive electrode 2 extending out of the cover 24 . The sealing cap 26 needs to have good electrical conductivity and chemical stability. In addition, the sealing cap 26 can also prevent the water-based electrolyte from evaporating through the hole passing through the positive electrode 2 , thereby reducing the consumption of the water-based electrolyte 6 . The positive pole 2 is connected with an external circuit.

The negative electrode 4 also extends out of the cover body 24 so as to be connected to an external circuit. Likewise, a sealing cap (not shown) is provided at the end of the negative electrode 4 extending out of the cover 24 .

In addition, during the charging process of the battery 1, especially when it is approaching the late stage of charging, due to the decomposition of the aqueous electrolyte 6, hydrogen and oxygen gas will be generated, and the pressure in the battery case will also rise. When the pressure rises to a certain value, the battery case will Body 22 deforms. Therefore, the battery 1 also includes a safety valve 28 for controlling the pressure inside the casing 22 . When the pressure in the casing 22 of the battery reaches the preset valve opening pressure, the safety valve 28 opens to release the pressure and prevent the casing 22 from deforming, thereby improving the life and safety of the battery 1 .

In addition, when the pressure inside the casing 22 reaches the preset valve closing pressure, the safety valve 28 is closed to prevent the internal gas from leaking out. At the same time, it also prevents external air from entering the casing 22 and causing adverse effects. Moreover, it can also prevent the precipitated hydrogen from flashing back when it encounters an open flame, thereby detonating the gas inside the shell 22 .

A liquid replenishment port (not shown) for replenishing the aqueous electrolyte 6 may also be provided on the casing 22 . In this way, when the aqueous electrolyte is consumed, the electrolyte can be injected through the liquid replenishment port.

Preferably, the liquid replenishment port is an installation hole (not shown) where the safety valve 28 is installed.

The positive electrode 2 is arranged between two negative electrodes 4, and an aqueous electrolyte 6 is arranged between the positive electrode 2 and the negative electrode 4. The positive electrode 2 includes a composite current collector 8 and a positive electrode active material 10, and the composite current collector 8 has a first surface 81 oppositely arranged. and the second surface 82 , the positive electrode active material 10 is disposed on the first surface 81 and the second surface 82 , as shown in FIG. 2 .

The manufacturing method of the positive electrode 2 is not particularly limited. The positive electrode active material 10 can be attached to the composite current collector 8 by coating, for example, the positive electrode active material 10 is made into a slurry, and then coated on the composite current collector by a slurry drawing method. 8; the positive electrode active material 10 can also be attached to the composite current collector 8 by lamination, for example, the composite current collector 8 and the positive electrode active material 10 formed in a predetermined size are pressed, so that the positive electrode active material 10 and the composite current collector The electrical contact between 8 is good, and the positive electrode 2 is formed. The coating density of the positive electrode active material 10 is in the range of 100-1000 g/m ² .

Specifically, the positive active material 10 has a spinel structure, a layered structure or an olivine structure.

Specifically, the positive electrode active material 10 is capable of reversible extraction-intercalation of lithium ions, sodium ions or magnesium ions.

The positive electrode active material 10 may be a compound with a spinel structure conforming to the general formula Li _{1+x Mny} M _z O _k capable of reversibly extracting and intercalating lithium ions, wherein -1≤x≤0.5, 1≤y≤2.5, 0≤z≤0.5, 3≤k≤6, and M is at least one selected from Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, and Ni. Preferably, the positive electrode active material contains LiMn ₂ O ₄ . More preferably, the positive electrode active material contains LiMn ₂ O ₄ that has been modified by doping or coating.

The positive electrode active material 10 may be a compound with a layered structure capable of reversibly extracting and intercalating lithium ions according to the general formula Li _1+x M _y M' _z M" _c O _2+n , where -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, At least one of Zr, Si or Al. Preferably, the positive electrode active material contains LiCoO ₂ .

The positive electrode active material 10 may be a compound with an olivine structure conforming to the general formula Li _x M _1-y M' _y (XO ₄ ) _n capable of reversibly extracting and intercalating lithium ions, where 0<x≤2, 0≤y≤ 0.6, 1≤n≤1.5, M is selected from Fe, Mn, V or Co, M' is selected from at least one of Mg, Ti, Cr, V or Al, X is selected from at least one of S, P or Si kind. Preferably, the positive electrode active material contains LiFePO ₄ .

At present, in the lithium battery industry, almost all positive electrode active materials are modified by doping and coating. However, doping, coating modification and other means make the general chemical formula expression of the material complex. For example, LiMn ₂ O ₄ can no longer represent the general formula of "lithium manganese oxide" widely used at present, but should be represented by the general formula Li _1+x Mn _y M _z O _k shall prevail, and widely include various modified LiMn ₂ O ₄ cathode active materials. Similarly, LiFePO ₄ and LiCoO ₂ should also be broadly understood as including those modified by various doping, coating, etc., and the general formulas correspond to Li _x M _1-y M′ _y (XO ₄ ) _n and Li ₁₊ The positive electrode active material of _x M _y M′ _z M″ _c O _2+n .

When the positive electrode active material 10 is a lithium ion deintercalation-intercalation compound, compounds such as LiMn ₂ O ₄ , LiFePO ₄ , LiCoO ₂ , LiM _x PO ₄ , LiM _x SiO _y (wherein M is a variable-valence metal) can be selected.

In addition, the compound NaVPO ₄ F that can extract-intercalate sodium ions, the compound MgM _x O _y that can extract-intercalate magnesium ions (where M is a metal, 0.5<x<3, 2<y<6) and have similar functions , compounds capable of extracting-intercalating 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 lithium-ion batteries.

In a specific embodiment, when preparing the positive electrode, a binder is also added to the positive electrode slurry, and the binder is beneficial to uniformly bond the positive electrode active material 10 together. The weight percentage range of the solid content of the binder in the positive electrode slurry is 0.5-10%. Specifically, the binder is selected from but not limited to polymers, and the polymers are selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose At least one of derivatives (CMC derivation), styrene-butadiene rubber (SBR), and styrene-butadiene rubber derivatives (SBR derivation). Styrene-butadiene rubber derivatives such as hydrophilic styrene-butadiene rubber (PSBR100) obtained through chemical modification.

In a specific embodiment, when preparing the positive electrode, a conductive agent is also added to the positive electrode slurry. The conductive agent mainly plays a role in improving the electron-conducting ability of the positive electrode active material 10. The weight percentage of the solid content of the conductive agent in the positive electrode slurry is The range is 0.5-30%. The conductive agent includes at least one selected from conductive polymers, carbon nanotubes, activated carbon, graphene, carbon black, graphite, carbon fibers, and conductive ceramics. Carbon black includes but not limited to acetylene black, Ketjen black (KB) and super-p black. The conductive agent may also include metal oxides. Metal oxides include, but are not limited to, lead oxide and tin oxide.

FIG. 2 is a schematic diagram of a composite current collector 8 . The composite current collector 8 includes a positive electrode current collector 12 and a conductive film 14 coated on the positive electrode current collector 12 .

The conductive film 14 coated on the positive electrode current collector 12 must be stable in the aqueous electrolyte, insoluble in the electrolyte, not swollen, not oxidized by high voltage, and easy to process into a dense, water-impermeable and conductive film. On the one hand, the conductive film can protect the positive electrode collector and avoid the corrosion of the positive electrode collector by the aqueous electrolyte. On the other hand, it is beneficial to reduce the contact internal resistance between the positive electrode active material and the positive electrode current collector, and improve the energy of the battery.

In order to effectively play the role of the conductive film 14, the thickness of the conductive film 14 needs to be effectively controlled. If the thickness of the conductive film 14 is too thin, it is easy to be damaged, and the thickness uniformity is not good, and the aqueous electrolyte 6 is easy to penetrate; if the conductive film 14 is too thick, the conductivity will be affected. Preferably, the thickness of the conductive film 14 is 10 μm-2 mm. The conductive film 14 can not only effectively protect the positive electrode collector 12 , but also help reduce the internal contact resistance between the positive electrode active material 10 and the positive electrode collector 12 .

The positive current collector 12 has a first surface and a second surface opposite to each other. Preferably, both the first surface and the second surface of the positive current collector 12 are coated with a conductive film 14 .

The conductive film 14 can be coated on the positive electrode current collector 12 by adhesive bonding, thermocompression lamination, or vacuuming. For example, the positive electrode current collector 12 is placed between two conductive films 14 and combined by heating. Make the conductive film 14 cover the positive electrode collector 12 , and ensure that the portion of the conductive film 14 that is larger than the positive electrode collector 12 is well sealed.

The conductive film 14 includes a polymer as an essential component, and the polymer accounts for 50-95% by weight of the conductive film. Preferably, the polymer is selected from thermoplastic polymers. In order to make the conductive film conductive, there are two possible forms: (1) the polymer is a conductive polymer; (2) the conductive film also contains conductive fillers.

The material selection of the conductive polymer is required to be conductive but electrochemically inert, that is, it will not conduct ion conduction as a charge transfer medium. Specifically, the conductive polymer includes but not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, polyquinoline, polyparaphenylene and any mixture thereof. Conductive polymers are inherently conductive, but conductive polymers can also be doped or modified to further improve their conductivity. From the consideration of conductive performance and stable use in batteries, the conductive polymers are preferably polyaniline, polypyrrole, polythiophene and polyacetylene.

Similarly, the material selection requirements for conductive fillers are small surface area, difficult to oxidize, high crystallinity, electrical conductivity but electrochemical inertness, that is, ion conduction that does not act as a charge transfer medium.

Materials for conductive fillers include, but are not limited to, conductive polymers, carbon-based materials, or metal oxides. The mass percent range of the conductive filler in the conductive film is 5-50%. The average particle size of the conductive filler is not particularly limited, and generally ranges from 100 nm to 100 μm.

Preferably, the conductive filler is a carbon-based material, and there is no special requirement on the form or mechanical properties of the carbon-based material. For example, the carbon-based material is selected from graphite, carbon nanotubes or amorphous carbon. Amorphous carbon includes, but is not limited to, activated carbon and carbon black. The carbon-based materials are preferably carbon black and graphite, which have a large potential window and thus are stable to a wide range of positive and negative electrode potentials and have high conductivity. Metal oxides include but are not limited to lead oxide, tin oxide.

When the conductive film contains conductive fillers, the polymer in the conductive film preferably contains a non-conductive polymer that binds the conductive filler. The non-conductive polymer enhances the bonding of the conductive filler and improves the reliability of the battery. Preferably, the non-conductive polymer is a thermoplastic polymer.

Specifically, thermoplastic polymers include but are not limited to polyolefins such as polyethylene, polypropylene, polybutylene, polyvinyl chloride, polystyrene, polyamide, polycarbonate, polymethyl methacrylate, polyoxymethylene, polystyrene One or more of ether, polysulfone, polyethersulfone, styrene-butadiene rubber or polyvinylidene fluoride. Among them, polyolefin, polyamide, and polyvinylidene fluoride are preferable. These polymers are easily melted by heat, and thus are easily composited with the positive electrode current collector and the positive electrode sheet. In addition, these polymers have a large potential window, which stabilizes the cathode and saves weight for the battery output density.

Specifically, the conductive film may be formed by preparing a slurry containing a thermoplastic polymer and coating and curing the slurry. Of course, the conductive filler can be additionally included in the slurry. Specifically, the polymer and the conductive filler are processed in a certain compounding manner, such as dispersion compounding and hierarchical compounding, to obtain a conductive film with conductive properties. Preferably, the polymer monomer and the conductive filler are mixed. Since the polymer monomer is a small molecule, the conductive filler can be well dispersed in the polymer monomer, and then the polymer monomer is polymerized under the action of the initiator , to prepare a conductive film.

The positive current collector 12 is mainly used as a carrier for electron conduction and collection, and does not participate in the electrochemical reaction, that is, within the working voltage range of the battery 1, the positive current collector 12 can stably exist in the aqueous electrolyte 6, thereby ensuring that the battery 1 has a stable cycle performance. The positive current collector 12 needs to meet the requirements of large surface area, good mechanical properties, and good electrical conductivity. The material of the positive current collector 12 includes one of carbon-based material, metal or alloy.

The carbon-based material is selected from one of glassy carbon, graphite foil, graphite sheet, foamed carbon, carbon felt, carbon cloth, and carbon fiber. In a specific embodiment, the positive electrode current collector is graphite, such as a commercial graphite-pressed foil, wherein the weight ratio of graphite is in the range of 90-100%.

The metal includes Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or one of the above-mentioned metals after passivation treatment. In a specific embodiment, the positive current collector 12 is nickel foam. The composite current collector containing foamed nickel is not easily corroded in the aqueous electrolyte 6, so that the performance of the positive electrode 2 containing this composite current collector 8 is more stable.

The main purpose of passivating the metal is to form a passivation film on the surface of the metal, so that it can collect and conduct electrons stably during the charging and discharging process of the battery without participating in the positive electrode reaction, ensuring that the battery performance.

The alloys include stainless steel, carbon steel, Al alloys, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-Rh alloys or one of the above-mentioned metals after passivation treatment.

Stainless steel includes stainless steel mesh and stainless steel foil, and the type of stainless steel includes but is not limited to one of stainless steel 304, stainless steel 316, or stainless steel 316L.

Similarly, the passivation treatment of stainless steel is also to enable it to collect and conduct electrons stably without participating in the electrode reaction to ensure battery performance. In a specific embodiment, the specific process of passivating stainless steel is: placing the stainless steel in 20% nitric acid at 50°C for half an hour to form a passivation film on the surface of the stainless steel. Passivated stainless steel is used as a current collector.

The thickness of the positive electrode current collector 12 has a certain influence on the electrochemical performance of the positive electrode 2. If the thickness of the positive electrode current collector 12 is too thin, it will affect the mechanical strength of the positive electrode current collector 12; Weight, thereby affecting the energy density of the positive electrode 2, in the present invention, in order to make the battery have a high energy density output, preferably, the thickness of the positive electrode current collector 12 is 10 μm-100 μm.

Preferably, before using the positive electrode current collector 12, the positive electrode current collector 12 is subjected to passivation, punching, grinding or weak acid corrosion treatment, and the treated positive electrode current collector 12 has a larger specific surface area, which is conducive to improving the positive electrode current collector 12 and The degree of recombination of the conductive film 14 reduces the contact internal resistance between the positive electrode active material 10 and the composite current collector 8 .

In the present invention, the positive electrode 2 uses a composite current collector 8, that is, a conductive film 14 is coated on the surface of the positive electrode current collector 12, and the conductive film 14 is made of a polymer or composite polymer with excellent electrical conductivity. On the one hand, the conductive film 14 can Further improve the electron conduction capability of the positive electrode collector 12, thereby improving the high rate performance of the battery; on the other hand, the conductive film 14 coated on the positive electrode collector 12 avoids direct contact between the positive electrode collector 12 and the aqueous electrolyte 6, solving The potential corrosion problem of the aqueous electrolyte 6 on the positive electrode collector 12 is eliminated, the stability of the positive electrode collector 12 is ensured, and the possible self-discharge problem of the battery 1 is solved, so that the battery 1 has a stable cycle performance.

The negative electrode 4 is selected from metals, alloys or carbon-based materials, and the thickness of the negative electrode current collector ranges from 20 to 500 μm.

Specifically, the negative electrode 4 is selected from at least one of metals Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al, or passivated metals, or at least one of alloys containing the above metals, or graphite At least one of foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or tinned copper, or brass.

In one embodiment of the negative electrode 4, the negative electrode 4 only includes a negative electrode current collector, and the negative electrode current collector acts as a carrier for electron conduction and collection, and does not participate in electrochemical reactions. The material of the negative electrode current collector is selected from but not limited to metal Cu, Ag, Pb, Sn, Fe, Al or at least one of the above-mentioned metals after passivation treatment, or carbon-based material, or stainless steel. Wherein, the carbon-based materials include graphite materials, such as commercial graphite-pressed foils, wherein the weight ratio of graphite is in the range of 90-100%. Stainless steel materials include but not limited to stainless steel 304 or stainless steel 316 or stainless steel 316L.

Negative electrode 4 can also be selected from metals containing plating/coating with high hydrogen evolution potential, thereby reducing the occurrence of negative electrode side reactions. Plating/coating is at least one selected from simple substances, alloys, or oxides containing C, Sn, In, Ag, Pb, Co, and Zn. The thickness of plating/coating ranges from 1-1000nm. For example: plating lead or silver on the surface of the negative electrode collector of copper, or covering a layer of carbon in the form of coating.

In another embodiment of the negative electrode 4, the negative electrode 4 only includes the negative electrode current collector, but the material selection of the negative electrode current collector corresponds to the active ions in the electrolyte, that is, the material of the negative electrode current collector is a simple substance of active ions, such as the active ion in the electrolyte. The ions are Zn ²⁺ , and the negative electrode 4 corresponds to metal Zn. At this time, the negative electrode 4 not only acts as a deposition carrier for active ions, but also participates in battery reactions.

In another embodiment of the negative electrode 4, the negative electrode 4 includes a negative electrode current collector and a negative electrode active material, and the material selection of the negative electrode active material corresponds to the active ions in the electrolyte, that is, the material of the negative electrode active material is a simple substance of active ions, such as an electrolyte The middle active ion is Zn ²⁺ , and the negative active material corresponds to metal Zn. Exemplarily, the negative electrode 4 includes brass foil and zinc foil, the brass foil serves as the negative electrode collector, and the zinc foil corresponds to the negative electrode active material, which can participate in the reaction of the negative electrode 4 .

The aqueous electrolyte 6 includes an electrolyte, and the electrolyte can at least ionize active ions, and the active ions are reduced and deposited on the negative electrode 4 during charging to form a negative active material (not shown), and the negative active material is oxidized and dissolved in the aqueous electrolyte 6 during discharge. middle.

The active ions include metal ions, and the metal is selected from at least one of Zn, Fe, Cr, Cu, Mn, Ni, and Sn. In a preferred embodiment, the active ion is Zn ²⁺ . The concentration range of active ions is 0.5-15mol/L.

More preferably, the aqueous electrolyte solution 6 further includes an electrolyte, which can ionize ions corresponding to reversible deintercalation at the positive electrode.

The aqueous electrolytic solution 6 contains ions capable of reversible extraction-intercalation, so that the ion exchange rate between the positive electrode active material 10 and the aqueous electrolytic solution 6 can be increased. Specifically, the positive electrode active material 10 is a compound capable of reversibly extracting and intercalating lithium ions, and the corresponding electrolyte also includes a lithium salt capable of ionizing lithium ions. The reversible detachment-intercalation ions include lithium ions, sodium ions or magnesium ions, and the concentration range of the reversible detachment-intercalation ions in the aqueous electrolyte is 0.1-10mol/L.

The active ions exist in the aqueous electrolyte in the form of at least one of hydrochloride, sulfate, acetate, nitrate or formate.

In order to ensure the battery capacity, the concentration of active ions in the aqueous electrolyte 6 must reach a certain range. When the aqueous electrolyte is too alkaline, the solubility of active ions in the electrolyte will be affected; when the aqueous electrolyte is too acidic, electrodes will appear. Material corrosion and proton co-intercalation during charge and discharge, etc., therefore, the pH range of the aqueous electrolyte is 3-7.

The diaphragm 16 is arranged between the positive electrode 2 and the negative electrode 4. On the one hand, the diaphragm 16 prevents the short circuit of the battery 1; After being stacked and arranged with the negative electrode 4, it is placed in the casing 22, and a certain amount of water-based electrolyte 6 is injected and packaged. The diaphragm 16 is soaked in the water-based electrolyte 6, that is, the water-based electrolyte 6 is absorbed in the diaphragm 16, ensuring The ion conduction path between the positive electrode 2 and the negative electrode 4; in addition, the separator 16 can also be soaked in the aqueous electrolyte 6 first, and then the separator 16 that has absorbed the aqueous electrolyte 6 is placed on the positive electrode 2 and the negative electrode 4 between.

As the separator 16, a porous separator, non-woven fabric, or glass fiber can be used. The porous diaphragm includes but not limited to polyethylene (PE), polypropylene (PP), one of polyimides, or a laminated diaphragm of PE-PP, PP-PE-PP. Nonwovens include, but are not limited to, rayon, acetate, and nylon. The impregnation amount of the water-based electrolyte in the diaphragm can be within the range of the holding capacity of the diaphragm, or can exceed the holding range, because the battery 1 is provided with a casing, which can prevent the leakage of the water-based electrolyte 6 .

1 and 3, the positive electrode 2 is stacked between the negative electrodes 4, the negative electrodes 4 share the positive electrode 2, electrons are exported or imported from the positive electrode current collector 12 and the negative electrode 4, and the battery 1 is equivalent to the interior of two battery cells 20 In parallel, each battery cell 20 has a positive electrode 2 , a negative electrode 4 , an aqueous electrolyte 6 and a diaphragm 16 , and the diaphragm 16 holds the aqueous electrolyte 6 . In the battery structure provided by the present invention, since the battery cells 20 are connected in parallel, the aqueous electrolyte 6 can shuttle through any battery cell 20 without causing a short circuit of the battery cells 20, and the battery 1 can work normally and stably.

The charging and discharging principle of the battery provided by the present invention is: in a battery unit 20, when charging, the positive electrode active material 10 capable of reversibly extracting and intercalating ions extracts the ions, and at the same time, the active ions in the aqueous electrolyte 6 are obtained from the negative electrode 4. The electrons are reduced and deposited on the negative electrode 4 to form the negative electrode active material. The discharge process is the reverse process of charging.

In the present invention, the positive electrode 2 uses a composite current collector 8, and the conductive film 14 coated on the positive electrode current collector 12 is equivalent to a protective film, which can effectively prevent the corrosion of the positive electrode current collector 12 by the aqueous electrolyte 6 and improve the self-discharge of the battery 1. Impact. In addition, compared with the prior art battery composed of independent battery cells connected in parallel, in the present invention, only one positive electrode 2 is cleverly used to form a battery 1 with a parallel structure, and two negative electrodes 4 share one positive electrode 2, making full use of The first surface 81 and the second surface 82 of the composite current collector 8 are removed, and the positive electrode active material 10 is arranged on the first surface 81 and the second surface 82 at the same time, which not only saves the positive electrode material, but also makes the structure of the battery 1 more compact and lightens the The weight of the battery 1 is reduced, so the battery 1 of the present invention has excellent energy density and power density. In addition, the battery 1 in the present invention uses the aqueous electrolyte 6 , which is safer and more environmentally friendly than the current commercial lithium-ion battery using the organic electrolyte.

The battery preparation process in the present invention is simple, and the battery can be prepared by stacking. Specifically, the negative electrode, the separator soaked in the aqueous electrolyte, the positive electrode and the negative electrode are arranged in a row in a stack in sequence, and then they can be packaged. The battery 1 is equivalent to two battery cells 20 formed in parallel, and there is no special sealing member between the battery cells 20 and the battery cells 20. The battery 1 with this internal parallel structure can work normally and stably, and has excellent charge and discharge performance. Moreover, the battery 1 can output higher capacity, and the battery 1 is widely used.

Implementation mode two

Please refer to FIG. 4 , Embodiment 2 provides a battery 30 , including a casing 22 , two positive electrodes 2 , a negative electrode 4 , an aqueous electrolyte 6 and a separator disposed in the casing 22 . The positive electrode 2 and the negative electrode 4 are stacked and arranged in the casing 22, the negative electrode 4 is arranged between the two positive electrodes 2, the two positive electrodes 2 share the negative electrode 4, and a diaphragm is arranged between the negative electrode 4 and the positive electrode 2, and the diaphragm holds the aqueous electrolyte.

The positive electrode 2 includes a composite current collector 8 and a positive electrode active material 10 , and the composite current collector 8 includes a positive electrode current collector 12 and a conductive film 14 coated on the positive electrode current collector. The composite current collector 8 has a first surface 81 and a second surface 82 oppositely arranged, the first surface 81 is opposite to the negative electrode 4, and the positive electrode active material 10 is arranged at least on the first surface 81, of course, there is no particular limitation, the positive electrode active material 10 can also be disposed on the second surface 82 at the same time, as shown in FIG. 5 . The negative electrode 4 is selected from metal, alloy or carbon-based materials; the aqueous electrolyte includes an electrolyte, and the electrolyte can at least ionize active ions, and the active ions are reduced and deposited on the negative electrode 4 during charging to form a negative active material (not shown), and the negative active material It is oxidized and dissolved in the aqueous electrolyte solution 6 during discharge.

The positive electrode active material 10 , the composite current collector 8 , the negative electrode and the aqueous electrolyte 6 have already been introduced in Embodiment 1, and will not be repeated here.

Similarly, the conductive film 14 can further improve the conductivity of the positive electrode collector 12 on the one hand, and the conductive film 14 on the other side mainly isolates the contact between the positive electrode collector 12 and the water-based electrolyte 6, thereby avoiding the water-based electrolyte 6 to the positive electrode collector 12. Corrosion, to ensure the stability of the positive electrode collector 12.

The casing 22 can be configured in a square or cylindrical shape, and correspondingly, the battery 30 can be designed as a square battery or a cylindrical battery.

Specifically, the positive electrode 2 , the separator 16 , the negative electrode 4 , the separator 16 and the positive electrode 2 are stacked and arranged to form a flat plate, and placed in the casing 22 , as shown in FIG. 4 . Therefore, the battery 30 can be designed as a square battery, such as a rectangular parallelepiped or a cube. The battery has the advantages of simple structure, convenient manufacture and low cost.

In addition, the positive electrode 2 , the separator 16 , the negative electrode 4 , the separator 16 and the positive electrode 2 are stacked to form a flat plate, and then wound to form a flat cell. Preferably, the positive electrode 2, the separator 16 and the negative electrode 4 are all arranged in a strip shape. According to the design of the battery, it needs to be wound into different numbers of turns.

The housing 22 can also be configured in a cylindrical shape.

Specifically, the positive electrode 2, the separator 16, the negative electrode 4, the separator 16, and the positive electrode 2 are stacked and arranged to form a flat plate, and then a cylindrical cell is formed by winding and placed in the casing 22. The positive electrode 2, the separator 16, the negative electrode 4 and the shell The bodies 22 are arranged coaxially. Therefore, the battery can be designed as a cylindrical battery, and the battery has a simple structure and is convenient to manufacture.

The rest of the configuration of the battery 30 in the second embodiment is the same as that in the first embodiment, and will not be repeated here.

The batteries in the first and second embodiments are equivalent to two battery cells connected in parallel. The difference is that the battery 1 in the first embodiment has two negative electrodes 4 sharing one positive electrode 2, while the battery 30 in the second embodiment has two positive electrodes. 2 share one negative electrode 4. Therefore, the battery provided by the present invention has flexible options. When actually manufacturing the battery, factors such as the manufacturing process, the weight of the positive and negative electrodes, and the cost of materials can be selected and manufactured as described in Embodiment 1 or 2. The battery with the shown structure makes the final battery more cost and performance advantages.

In the battery of the present invention, the positive electrode adopts a composite current collector, that is, a positive electrode current collector coated with a conductive film is used, and the conductive film is used as a protective film of the positive electrode current collector to prevent the corrosion of the positive electrode current collector by the aqueous electrolyte and improve the potential of the battery. Self-discharge problem, the battery has a stable cycle performance. The battery has an internal parallel structure. Compared with the parallel structure battery in the prior art, the battery in the present invention is more material-saving and compact and lightweight, so that the battery in the present invention has obvious advantages in energy density and volume; secondly , the battery uses water-based electrolyte, which has relatively higher ionic conductivity, which improves the rate performance of the battery; the battery is safe to use, environmentally friendly and has a simple manufacturing process. During the preparation process, it can be prepared according to the use requirements. The battery has a wide range of uses and has industrial application prospects.

Implementation Mode Three

Please refer to FIG. 6 , a battery 40 includes a casing 22 , a positive electrode 2 , a negative electrode 4 , an aqueous electrolyte 6 and a diaphragm arranged in the casing 22 .

The battery includes n pairs of positive poles 2 and negative poles 4, n≥2, positive poles 2 and negative poles 4 are arranged alternately, two adjacent positive poles 2 share the negative pole 4 between the two positive poles 2, and two adjacent negative poles 4 share the Positive pole 2 between two negative poles 4. Specifically in FIG. 6 , the battery 300 includes two pairs of positive poles 2 and negative poles 4 , two adjacent positive poles 2 share the negative pole 4 between the two positive poles 2 , and two adjacent negative poles 4 share the same negative pole 4 between the two negative poles 4 Between the positive pole 2.

The positive electrode 2 includes a composite current collector 8 and a positive electrode active material 10. The composite current collector 8 includes a positive electrode current collector 12 and a conductive film 14 coated on the positive electrode current collector 12. The composite current collector 8 has two opposite sides, wherein at least the composite A positive electrode active material 10 is provided on the side of the current collector 8 opposite to the negative electrode 4, and the positive electrode active material can reversibly extract and intercalate ions.

Specifically, as shown in FIG. 6, the positive electrode composite current collector 8 has two opposite sides. When the positive electrode 2 is located between two negative electrodes 4, the two opposite sides of the composite current collector 8 are opposite to the negative electrode 4. Therefore, the composite current collector The positive electrode active material 10 needs to be arranged on both sides of the fluid 8 opposite to each other; and for the positive electrode 2 located in the outermost layer, only one side of the composite current collector 8 is opposite to the negative electrode 4, so at least one side of the composite current collector 8 is opposite to the negative electrode 4. The positive electrode active material 10 is set, and the side of the composite current collector 8 opposite to the negative electrode 4 is not particularly limited, and the positive electrode active material can be selectively set according to the actual manufacturing process. It is roughly shown in FIG. 7 that it is located in the outermost positive electrode. The positive electrode active material 10 is also provided on the side of the composite current collector opposite to the negative electrode.

The negative electrode 4 is selected from metal, alloy or carbon-based materials; the aqueous electrolyte includes an electrolyte, and the electrolyte can at least ionize active ions, and the active ions are reduced and deposited on the negative electrode 4 during charging to form a negative active material (not shown), and the negative active material It is oxidized and dissolved in the aqueous electrolyte solution 6 during discharge. The material selection and manufacturing method of the positive electrode, the negative electrode and the aqueous electrolyte in Embodiment 3 are the same as those in Embodiment 1, and will not be repeated here.

The battery 40 shown in Figure 6 contains two pairs of positive and negative poles, which is equivalent to three battery cells (not shown) connected in parallel, but when actually making the battery, the battery structure provided by the present invention can easily increase the positive pole according to the use requirements , or the negative pole, or the positive pole and the negative pole, such as stacking the negative pole at the positive pole of the outermost layer of the battery 40, or stacking the negative pole and the positive pole in sequence, or superimposing the positive pole at the negative pole of the outermost layer of the battery 40, or stacking the positive pole and the negative pole in sequence, stacking The positive and negative electrodes are arranged alternately. The number of positive and negative electrodes is determined according to the usage requirements. As shown in FIG. 8, although the total output voltage of the battery 50 has not changed, the battery 50 has a higher capacity, flexible battery structure, wide range of uses, and has industrial application prospects.

In a battery system containing a neutral aqueous electrolyte, it is difficult to find a positive electrode current collector that satisfies both certain mechanical properties and excellent electrical conductivity, and can exist stably in a neutral aqueous electrolyte. Therefore, the commercialization of aqueous batteries The process has been stalled. The battery provided by the present invention can just solve this problem. The positive electrode of the battery adopts a composite current collector, and the composite current collector adopts a positive electrode current collector coated with a conductive film. On the one hand, the conductive film can improve the conductivity of the positive electrode current collector. More importantly, It protects the positive current collector, isolates the corrosion of the positive current collector by the neutral aqueous electrolyte, and enables the positive current collector to collect and export electrons stably during the discharge process, thereby ensuring that the battery has a stable cycle performance. The invention provides The battery has a good commercialization prospect.

【Bipolar battery】

The present invention also provides a battery, specifically, the battery is an aqueous bipolar battery. The water-based bipolar battery will be described below through specific implementation methods.

Implementation Mode Four

Please refer to FIGS. 9 and 10, a battery 100 includes a casing (not shown), a positive lead-out electrode 54, at least one bipolar electrode 52, a negative lead-out electrode 58 and an aqueous electrolyte disposed in the casing. 6. The positive lead-out electrode 54, the bipolar electrode 52 and the negative lead-out electrode 58 are stacked and arranged in the casing, the positive lead-out electrode 54 and the negative lead-out electrode 58 are respectively located at the uppermost layer and the lowermost layer, and the bipolar electrode 52 and the aqueous electrolyte 6 are arranged Between the positive extraction electrode 54 and the negative extraction electrode 58 . Referring specifically to FIG. 9 , battery 100 includes two bipolar electrodes 52 .

The housing can be configured as a square. Specifically, the positive lead-out electrode 54 , the bipolar electrode 52 and the negative lead-out electrode 58 are stacked and arranged to form a flat plate, and placed in the casing. Therefore, the battery 100 can be designed as a square battery, such as a rectangular parallelepiped or a cube. The battery 100 is simple in structure, convenient to manufacture, and low in cost.

The material selection and arrangement of the casing are the same as in Embodiment 1. Similarly, the battery 100 in Embodiment 4 also includes a cover (not shown) connected to the casing, and the positive lead-out electrode 54 and the negative lead-out electrode 58 extend through the cover. , is connected to the external circuit, and the end of the positive lead-out electrode 54 and the negative lead-out electrode 58 extending out of the cover is provided with a sealing cap, and the sealing cap can prevent the water-based electrolyte from passing through the holes of the positive lead-out electrode 54 and the negative lead-out electrode 58 evaporation, thereby reducing the consumption of the aqueous electrolyte 6.

Similarly, the battery 100 also includes a safety valve and a liquid replenishment port (not shown) provided on the housing. For the setting of the safety valve and the liquid replenishment port, refer to Embodiment 1, which will not be repeated here.

The positive lead-out electrode 54 includes a positive electrode collector 12 and a positive electrode active material 10 disposed on one side of the positive electrode collector 12 , and the positive electrode active material 10 is capable of reversibly extracting and intercalating ions. The positive electrode active material 10 and the positive electrode current collector 12 have already been introduced in the first embodiment, so the description will not be repeated here.

10 is a schematic cross-sectional view of a bipolar electrode 52 that constitutes a battery 100. The bipolar electrode 52 includes a bipolar current collector 56 and a positive electrode active material 10. The bipolar current collector 56 has a first face 61 and an oppositely arranged one. On the second surface 62 , the positive electrode active material 10 is disposed on the first surface 61 of the bipolar current collector 56 . The first surface 61 and the second surface 62 of the bipolar current collector 56 have opposite polarities, the first surface 61 corresponds to the positive electrode, and the second surface 62 corresponds to the negative electrode.

The manufacturing method of the bipolar electrode 52 is not particularly limited. The positive electrode active material 10 can be attached to the bipolar current collector 56 by coating, for example, the positive electrode active material 10 is made into a slurry, and then coated by a slurry drawing method. Covered on the bipolar current collector 56; the bipolar current collector 56 can also be coated on the pressed positive electrode active material 10; the positive electrode active material 10 can also be attached to the bipolar current collector 56 by lamination For example, the bipolar current collector 56 and the positive electrode active material 10 shaped according to a predetermined size are pressed, so that the electrical contact between the positive electrode active material 10 and the bipolar current collector 56 is good, and the bipolar electrode 52 is formed. The thickness of the positive electrode active material 10 is in the range of 100-400 μm. For the positive active material 10 in the bipolar electrode 52 and the positive active material 10 in the positive lead-out electrode 54 , please refer to the positive active material in Embodiment 1 for details.

The material of the bipolar current collector 56 can be conductive plastic, and preferably, the thickness of the bipolar current collector 56 ranges from 50 to 100 μm.

The conductive plastic material is selected from conductive polymers, specifically, conductive polymers include but are not limited to at least one of polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyquinoline or polyparaphenylene . Conductive polymers are inherently conductive, but conductive polymers can also be doped or modified to further improve their conductivity.

Conductive plastics can also be composite conductive plastics. Composite conductive plastics are formulated with polymers as the main matrix and mixed with conductive agents. Here, there is no special restriction on whether the polymer itself is conductive. The composite conductive plastics Conductivity is mainly achieved by conductive agent. Specifically, conductive plastics include polymers and conductive agents, and polymers include but are not limited to polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, polycarbonate, polymethyl methacrylate, At least one of polyoxymethylene, polyphenylene ether, polysulfone, polyethersulfone, styrene-butadiene rubber or fluororesin. Specifically, the polymer may be polytetrafluoroethylene in fluororesin, or a copolymer, such as a copolymer of polytetrafluoroethylene (PTFE) and styrene-butadiene rubber (SBR).

Conductive agents include carbon-based materials, metals or metal oxides. The mass percentage range of the conductive agent in the conductive plastic is 10-90%.

The carbon-based material is selected from one of graphite, carbon nanotubes or amorphous carbon. Amorphous carbon includes, but is not limited to, activated carbon and carbon black.

The form of the metal is not limited, and may be metal powder, metal flake, metal wire, metal fiber. Metal oxides include but are not limited to lead oxide, tin oxide.

Specifically, it is a plastic with conductive properties obtained by processing polymers and conductive agents in a certain compounding manner, such as dispersion compounding and hierarchical compounding.

The material of the bipolar current collector 56 can also be stainless steel or passivated stainless steel, the mechanical properties of stainless steel are better than conductive plastics, therefore, when using stainless steel as the bipolar current collector 56, the bipolar current collector 56 The thickness can be thinner, specifically, the thickness of the bipolar current collector 56 is in the range of 20-100 μm.

The method of passivation treatment of stainless steel is not limited, and may be passivation by physical method, passivation by chemical method or passivation by electrochemical method. The purpose of passivation is to improve the compatibility between the bipolar current collector 56 and the aqueous electrolyte 6 , thereby reducing the occurrence of side reactions and enabling the battery to have a stable cycle performance.

In the present invention, the mechanical performance requirements of the bipolar current collector 56 constituting the bipolar electrode 52 are not high, that is, lighter conductive plastic or thinner stainless steel can be used as the bipolar current collector 56, and the battery 100 The overall weight is reduced, so the energy density of the battery 100 is significantly increased.

The negative extraction electrode 58 is selected from metals, alloys, or carbon-based materials.

Specifically, the negative extraction electrode 58 is selected from at least one of metals Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al, or passivated metals, or at least one of alloys containing the above metals, Or at least one of graphite foil, graphite sheet, carbon cloth, carbon felt, carbon fiber, or tinned copper, or brass.

The negative lead-out electrode 58 can also be selected from metals containing plating/coating with high hydrogen evolution potential, thereby reducing the occurrence of negative side reactions. Plating/coating is at least one selected from simple substances, alloys, or oxides containing C, Sn, In, Ag, Pb, Co, and Zn. The thickness of plating/coating ranges from 1-1000nm. For example: lead or silver is plated on the surface of the copper negative lead-out electrode 58, or a layer of carbon is covered in the form of coating. The thickness range of the positive current collector 12 and the negative lead-out electrode 58 is 1-10 mm.

The negative electrode 58 is the same as the negative electrode 4 in the first embodiment, that is, the negative electrode 58 can only be used as a substrate for electron collection and conduction without participating in the electrode reaction, or the negative electrode 58 includes a negative current collector and a negative active material, such as a negative electrode 58 is brass foil and zinc foil, and the zinc foil is consistent with the negative electrode active material.

The aqueous electrolyte 6 is arranged between the positive lead-out electrode 54 and the negative lead-out electrode 58, and the positive lead-out electrode 54, the bipolar electrode 52 and the negative lead-out electrode 58 are stacked. When there is one bipolar electrode 52 in the battery 100, the positive An aqueous electrolyte 6 is provided between the extraction electrode 54 and the adjacent bipolar electrode 52 , and between the bipolar electrode 52 and the adjacent negative extraction electrode 58 . When there is more than one bipolar electrode 52 in the battery 100, between the positive lead-out electrode 54 and the adjacent bipolar electrode 52, between the adjacent bipolar electrodes 52, between the bipolar electrode 52 and the adjacent negative An aqueous electrolyte solution 6 is provided between the extraction electrodes 58 .

The aqueous electrolyte solution 6 includes an electrolyte, and the electrolyte can at least ionize active ions, and the active ions are reduced and deposited on the second surface of the bipolar current collector 56 during charging to form negative electrode active materials, and the negative electrode active materials are oxidized and dissolved in the water system during discharge. In the electrolytic solution 6, active ions exist in the aqueous electrolytic solution 6 in the form of at least one of hydrochloride, sulfate, acetate, nitrate or formate.

The aqueous electrolyte solution 6 and the active ions have been introduced in Embodiment 1, and will not be repeated here.

Preferably, the aqueous electrolyte solution 6 further includes ions corresponding to ions capable of reversible extraction-intercalation of the positive electrode active material 10, and the ions include at least one of lithium ions, sodium ions or magnesium ions. Specifically, when the positive electrode active material 10 can reversibly extract-intercalate lithium ions, then the corresponding aqueous electrolyte 6 also contains lithium ions, so that the ion exchange rate between the positive electrode active material 10 and the aqueous electrolyte 6 can be improved, and the The high rate charge and discharge performance of the battery 100.

The battery 100 in Embodiment 4 further includes a separator 16, which is arranged between the positive lead-out electrode 54 and the adjacent bipolar electrode 52, and between the bipolar electrode 52 and the adjacent negative lead-out electrode 58. The quadruple battery 100 includes two bipolar electrodes 52 , therefore, a separator 16 is also disposed between adjacent bipolar electrodes 52 . On the one hand, the separator 16 is used to hold the aqueous electrolyte solution 6 , and on the other hand, the separator 16 prevents the battery 100 from short circuiting.

As the separator 16, a porous separator, non-woven fabric, or glass fiber can be used. The porous diaphragm includes but not limited to polyethylene (PE), polypropylene (PP), one of polyimides, or a laminated diaphragm of PE-PP, PP-PE-PP. Nonwovens include, but are not limited to, rayon, acetate, and nylon. The impregnation amount of the aqueous electrolyte 6 in the diaphragm 16 may be within the holding capacity of the diaphragm 16 or may exceed the holding range, because the battery 100 is provided with a sealing portion 60 to prevent leakage of the aqueous electrolyte 6 .

The outer peripheral portion of the bipolar current collector 56 is provided with a sealing portion 60 for sealing the aqueous electrolyte 6. There is no particular limitation. The sealing portion 60 can be a sealing ring. The shape of the sealing ring is preferably rectangular. It is sufficient that an excellent sealing effect can be achieved under the usage environment of the battery 100 .

Not particularly limited, the material of the sealing part 60 is rubber, and the rubber is selected from but not limited to silicon rubber, fluorine rubber, olefin rubber, and nitrile rubber, wherein the olefin rubber includes but is not limited to styrene-butadiene rubber Rubber (SBR), Neoprene (CR). These rubber-based resins for sealing have good airtightness (liquid tightness), acid and alkali resistance, chemical resistance, durability, weather resistance, and heat resistance, and can maintain these properties for a long time under the environment in which the battery 100 is used. Excellent performance without deterioration, so it can effectively prevent the aqueous electrolyte 6 from seeping out of the battery 100, thereby preventing the short circuit of the battery 100 caused by the leakage of the aqueous electrolyte 6, and ensuring the cycle stability of the battery 100.

In addition, as long as the effect of the present invention can be effectively realized, various rubbers with acid resistance and sealing properties can be used as the material of the sealing part 60 of the present invention.

Not particularly limited, when the sealing part 60 adopts a sealing ring, the area of the diaphragm 16 is smaller than the surrounding area of the sealing ring, and the height of the sealing ring is not less than the sum of the thicknesses of the diaphragm 16 and the positive electrode active material 10. When assembling the battery, the The diaphragm 16 soaked with the water-based electrolyte 6 is placed in the ring of the sealing ring, and the diaphragm 16 does not participate in the sealing, so that the leakage of the water-based electrolyte 6 caused by the adoption of the porous diaphragm can be avoided. Of course, the area of the diaphragm 16 can also be larger than the surrounding area of the sealing portion 60 disposed on the outer periphery of the bipolar electrode 52 , as long as the diaphragm 16 and the sealing portion 60 are finally integrally formed so as not to cause leakage of the aqueous electrolyte 6 .

Please refer to Fig. 11, the bipolar electrode 52 is stacked between the positive lead-out electrode 54 and the negative lead-out electrode 58, electrons are only exported or imported from the positive lead-out electrode 54 and the negative lead-out electrode 58, and the battery 100 is equivalent to three The battery cells 64 are connected in series, and each battery cell 64 has a positive electrode, a negative electrode, an aqueous electrolyte, and a separator, and the aqueous electrolyte 6 is sealed by a sealing part 60 to avoid the leakage between the battery cells 64 due to the leakage of the aqueous electrolyte 6. Short circuit between them, so as to ensure the normal operation of the battery 100.

For example, one of the battery cells 64 includes the positive electrode current collector 12 , the positive electrode active material 10 , the separator 16 , the aqueous electrolyte 6 , the sealing portion 60 and the second surface 62 of the bipolar current collector 56 as the negative electrode. The sealing portion 60 is used to seal the aqueous electrolyte 6 in each battery cell 64 to avoid short circuit of the battery 100 caused by leakage of the aqueous electrolyte 6 . The battery 100 shown in FIG. 11 only includes two bipolar electrodes 52, but in fact, the number of bipolar electrodes 52 in the battery 100 can be easily set according to usage requirements, thereby preparing batteries with different output voltages As well as a battery with a high output voltage, the battery provided by the present invention has a wide range of applications.

The battery preparation process in the present invention is simple, and the battery can be prepared by stacking. Specifically, a rectangular sealing ring is stacked on the negative lead-out electrode, and the sealing ring is bonded to the outer periphery of the negative lead-out electrode, and then the ring A diaphragm soaked in an aqueous electrolyte is placed inside, and then a bipolar electrode and a positive lead-out electrode are stacked in sequence. The positive active material in the positive lead-out electrode and the bipolar electrode is placed toward the negative lead-out electrode at the same time, and the water-based electrolyte is sealed by a sealing ring. The number of bipolar electrodes determines the final output voltage of the battery. Therefore, the number of bipolar electrodes can be set according to the use requirements, and the battery has a wide range of uses.

Please refer to FIG. 12 , the charging and discharging principle of the battery 100 provided by the present invention is: in a battery cell 64, when charging, the ion can be extracted from the positive electrode active material 10 that can reversibly extract-intercalate the ion, and at the same time, the aqueous electrolyte 6 The active ions in the bipolar current collector 56 obtain electrons on the second surface 62 to be reduced and deposited on the second surface 62 to form negative electrode active materials. In the battery cell 64 including the negative extraction electrode 58 , active ions are reduced by obtaining electrons on the negative extraction electrode 58 and deposited on the negative extraction electrode 58 . The discharge process is the reverse process of charging.

In the present invention, the bipolar electrode 52 constituting the battery 100 is only provided with the positive electrode active material 10 on the first surface 61 of the bipolar current collector 56, while the second surface 62 of the bipolar current collector 56 is equivalent to the negative electrode, which is The active ions are electron reduction-deposited to provide a carrier, and the active ions are present in the aqueous electrolyte 6. Compared with the prior art, the positive electrode active material 10 is provided on the first surface 61 and the second surface 62 of the bipolar current collector 56, The structure of the battery 100 in the present invention is more compact, and the battery 100 has excellent energy density and power density. In addition, the battery 100 of the present invention uses the aqueous electrolyte 6 , which is safer and more environmentally friendly than the current commercial lithium-ion batteries using the organic electrolyte.

The battery 100 in the present invention is equivalent to a plurality of battery cells 64 formed in series, and each battery cell 64 is well sealed by the sealing part 60 to prevent short circuit caused by leakage of the aqueous electrolyte 6 . In addition, the battery of the present invention can prevent short-circuiting between battery cells without providing special leak-proof members or insulating members, thereby providing a bipolar battery having excellent ion conductivity and charge-discharge performance. In addition, different numbers of bipolar electrodes 52 can be set according to usage requirements, so as to prepare batteries 100 with different output voltages. The battery 100 has a wide range of uses.

Implementation Mode Five

Please refer to FIG. 13 , the fifth embodiment provides a battery 110. The battery 110 includes a casing (not shown), a positive lead-out electrode 54, at least one bipolar electrode 52, and a negative lead-out electrode 58 disposed in the casing. and aqueous electrolyte6. The bipolar electrode 52 is stacked between the positive lead-out electrode 54 and the negative lead-out electrode 58 , and the positive lead-out electrode 54 and the negative lead-out electrode 58 are respectively located at the uppermost layer and the lowermost layer.

The positive lead-out electrode 54 includes a positive electrode collector 12 and a positive electrode active material 10 disposed on one side of the positive electrode collector 12 . The difference from Embodiment 5 is that the positive electrode collector 12 is coated with a conductive film 14 .

The conductive film 14 can be coated on one side of the positive electrode current collector 12 by means of adhesive bonding, thermocompression lamination or vacuum coating, and then the positive electrode active material 10 is arranged on the conductive film 14. The thickness of the conductive film 14 is 0.01 -0.2mm. Specifically, in FIG. 13 , both surfaces of the positive electrode collector 12 are coated with a conductive film 14 .

The material of the conductive film 14 has been introduced in detail in the first embodiment, so it will not be repeated here.

On the one hand, using a conductive polymer or a compound containing a conductive agent as the conductive film 14 can improve the electron conductivity of the positive electrode collector 12; on the other hand, the conductive film 14 coated on the positive electrode collector avoids the positive electrode collector 12 is in direct contact with the water-based electrolyte 6, which solves the potential corrosion problem of the water-based electrolyte 6 on the positive electrode collector 12, ensures the stability of the positive electrode collector 12, and improves the possible self-discharge problem of the battery 110, so that the battery 110 has a stable cycle performance.

Please refer to FIG. 14 , the battery unit 68 is sealed by the sealing portion 60 , and the sealing portion 60 is disposed on the outer periphery of the bipolar current collector 56 for sealing the aqueous electrolyte 6 .

The other configurations and assembly methods of the battery 110 in the fifth embodiment are the same as those in the fourth embodiment, and will not be repeated here.

The battery provided in Embodiment 5 uses a positive electrode current collector coated with a conductive film, which eliminates the potential corrosion of the positive electrode current collector by the aqueous electrolyte, and enables the battery to further improve its performance in addition to the characteristics of high output voltage, safety, and environmental protection. cycle stability of the battery.

Embodiment six

Please refer to FIG. 15 , the sixth embodiment provides a battery 120, the battery 120 includes a casing (not shown), a positive lead-out electrode 54, at least one bipolar electrode 52, and a negative lead-out electrode 58 arranged in the casing and aqueous electrolyte6. The bipolar electrode 52 is stacked between the positive lead-out electrode 54 and the negative lead-out electrode 58 , and the positive lead-out electrode 54 and the negative lead-out electrode 58 are respectively located at the uppermost layer and the lowermost layer. The difference from Embodiment 4 is that the battery 120 does not include a separator.

Likewise, the battery cell (not shown) is sealed by a sealing portion 60 disposed on the outer periphery of the bipolar current collector 56 for sealing the aqueous electrolyte 6 . Exemplarily, the sealing part 60 can adopt a sealing ring, the height of the sealing ring is greater than the thickness of the positive electrode active material 10, through the sealing ring with a certain height, the bipolar collector between the positive lead-out electrode 54 and the adjacent bipolar electrode 52 A certain distance is maintained between the fluids 56 and between the bipolar current collector 56 of the bipolar electrode 52 and the adjacent negative lead-out electrode 58 to avoid a short circuit of the battery 120 . When there is more than one bipolar electrode 52 in the battery 120 , a sealing portion 60 is also provided between the bipolar current collectors 56 and the bipolar current collectors 56 of adjacent bipolar electrodes 52 .

When preparing the battery in Embodiment 6, the positive lead-out electrode 54 , the bipolar electrode 52 and the negative lead-out electrode 58 prepared according to predetermined specifications may be arranged and sealed. Specifically, the positive electrode active material 10 on the positive lead-out electrode 54 and the bipolar electrode 52 is arranged toward the negative lead-out electrode 58 at the same time, and the sealing part 60 can adopt a rubber material such as a sealing ring with a thickness higher than the positive electrode active material 10, and the sealing ring It is arranged on the outer periphery of the bipolar current collector 56, and finally injects the aqueous electrolyte 6 by injection; the sealing part 60 can also be made of thermoplastic rubber material. Thermoplastic rubber material is arranged on the outer periphery, and one side is left open. After arranging the positive lead-out electrode 54, the bipolar electrode 52 and the negative lead-out electrode 58, the rubber is cured and molded by heating or heating and pressing, and then injected through the unsealed side. A predetermined amount of aqueous electrolyte 6, and finally all battery cells are completely sealed.

The other configurations and assembly methods of the battery 120 in the sixth embodiment are the same as those in the fourth embodiment, and will not be repeated here.

The battery 120 in the sixth embodiment does not use a diaphragm, and the battery 120 can not only provide normal and continuous work, but also has better energy density and specific power due to its lighter weight. In addition, when the battery 120 is manufactured, the sealing portion 60 can be easily formed to prevent a short circuit caused by leakage of the aqueous electrolytic solution 6 . The battery 120 can prevent the short circuit between the battery cells even if no special anti-leakage parts are provided, and the battery 120 has excellent cycle performance and cycle life.

Implementation Mode Seven

Please refer to FIG. 16 , the seventh embodiment provides a battery 130, the battery 130 includes a casing (not shown), a positive lead-out electrode 54, at least one bipolar electrode 52, and a negative lead-out electrode 58 arranged in the casing and aqueous electrolyte6. The bipolar electrode 52 is stacked between the positive lead-out electrode 54 and the negative lead-out electrode 58 , and the positive lead-out electrode 54 and the negative lead-out electrode 58 are respectively located at the uppermost layer and the lowermost layer.

The positive lead-out electrode 54 includes a positive current collector 12 and a positive active material 10 disposed on one side of the positive current collector 12 . The difference from Embodiment 6 is that the positive current collector 12 is coated with a conductive film 14 .

The material selection and forming method of the conductive film 14 are the same as those in Embodiment 1, and will not be repeated here.

In the battery 130 in Embodiment 7, the conductive film 14 coated on the positive electrode current collector 12 isolates the contact between the positive electrode current collector 12 and the aqueous electrolyte 6, improves the stability of the positive electrode current collector 12, thereby ensuring that the battery 130 has a stable cycle performance. The battery 130 without a diaphragm is lighter in weight, and provides excellent performance while being convenient for users to carry.

In the battery of the present invention, the bipolar current collector in the bipolar electrode can be made of conductive plastic or thinner stainless steel. While ensuring the normal operation of the battery, the weight of the battery is lighter, so that the battery in the present invention has a higher energy efficiency. It has obvious advantages in terms of density and volume; secondly, the battery uses an aqueous electrolyte, which has a relatively higher ion conductivity and improves the rate performance of the battery; the battery is safe to use, environmentally friendly, and the manufacturing process is simple. , batteries with different output voltages can be prepared according to usage requirements, the batteries have a wide range of uses and have industrial application prospects.

The present invention provides a battery containing a bipolar electrode, wherein only one side of the bipolar electrode is coated with a positive active material, and the side of the bipolar electrode opposite to that coated with the positive active material has no negative active material before the battery is charged and discharged for the first time , The active ions of the negative electrode exist in the aqueous electrolyte, and when the battery is charged, they are deposited on the side of the bipolar electrode that is not coated with the positive active material, and the battery has excellent cycle performance. At the same time, the battery uses a water-based electrolyte. Compared with the lithium-ion battery using an organic electrolyte, the battery in the present invention is safer and more environmentally friendly. In addition, batteries with different output voltages and high output voltages can be prepared by setting the number of bipolar electrodes. The batteries are widely used and the preparation process is simple, and the batteries have potential for commercial application.

【Plate structure battery】

The invention also provides a battery, which has a plate structure.

Embodiment eight

As shown in FIG. 17 , a battery 140 includes a casing 70 , a positive electrode 72 , a negative electrode 74 , a diaphragm 76 and an aqueous electrolyte 78 disposed in the casing 70 . And the separator 76 is disposed between the positive electrode 72 and the negative electrode 74 .

The positive electrode 72 includes a positive electrode current collector 80 and a positive electrode active material 82 participating in an electrochemical reaction. The positive electrode active material 82 includes a compound capable of reversibly extracting and intercalating ions; the negative electrode 74 is selected from metals, alloys or carbon-based materials; the aqueous electrolyte 78 includes an electrolyte , the electrolyte can at least ionize active ions, and the active ions are reduced and deposited on the negative electrode 74 during charging to form negative active materials, and the negative active materials are oxidized and dissolved in the aqueous electrolyte 78 during discharge.

The positive electrode 72 , the negative electrode 74 , the aqueous electrolyte solution 78 and the separator 76 are the same as those in Embodiment 1, so the description will not be repeated here.

The positive electrode 72 , the separator 76 and the negative electrode 74 are formed into a flat plate shape, and the separator 76 is located between the positive electrode 72 and the negative electrode 74 . Correspondingly, the casing 70 is set in a square shape. Therefore, the battery can be designed as a square battery, such as a rectangular parallelepiped or a cube. The battery has the advantages of simple structure, convenient manufacture and low cost.

The battery 140 is designed to be stacked. The positive electrode 72 , the separator 76 and the negative electrode 74 are stacked to form a flat plate, and the separator 76 is located between the positive electrode 72 and the negative electrode 74 . Correspondingly, the casing 70 is also set in a square shape.

Specifically in FIG. 17 , there are four positive electrodes 72 , five negative electrodes 74 , and the one closest to the housing 70 is the negative electrode 74 .

The battery can also be configured to include several individual battery cells including individual positive electrodes, separators and negative electrodes. The battery cells are connected in parallel. Independent battery units can be set to 2 to 10 groups. Of course, the independent battery units can also be arranged in different groups according to different needs, such as 12 groups or more. In addition, independent battery cells can also be connected in series as required.

The casing 70 can be configured as metal, plastic or a composite film of metal and plastic, such as steel, aluminum, acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), nylon or aluminum-plastic film and the like. Preferably, the casing 70 is set as an aluminum plastic film, so that the casing is relatively thin. While reducing the weight of the battery, it also increases the space inside the battery. The aluminum-plastic film includes a layer of aluminum sheet and a first layer of plastic sheet. Preferably, the aluminum-plastic film further includes a second layer of plastic sheet disposed on the other side of the aluminum sheet relative to the first layer of plastic sheet.

The battery further includes a cover 84 connected to the casing 70 , the positive current collector 80 extends through the cover 84 , and a sealing cap 86 is provided at the end of the positive current collector 80 extending through the cover 84 . The sealing cap 86 needs to have good electrical conductivity and chemical stability. In addition, the sealing cap 86 can also prevent the water-based electrolyte 78 from evaporating through the hole passing through the positive electrode current collector 80 , thereby reducing the consumption of the water-based electrolyte 78 . The positive electrode 72 is connected to an external circuit.

The negative electrode 74 also extends out of the cover 84 to be connected to an external circuit. Likewise, the end of the negative electrode 74 extending out of the cover 24 is provided with a sealing cap (not shown).

In addition, during the charging process of the battery, especially when it is approaching the late stage of charging, due to the decomposition of water by the charging current, a large amount of hydrogen and oxygen gas will be released. As more and more hydrogen and oxygen are produced, the pressure inside the battery casing is also rising. When the pressure rises to a certain value, the battery casing will deform. Accordingly, the battery also includes a safety valve 88 for controlling the pressure inside the housing 70 . When the pressure in the casing 70 of the battery reaches the preset valve opening pressure, the safety valve 88 opens to release the pressure and prevent the casing from deforming, thereby improving the life and safety of the battery.

In addition, when the pressure inside the housing 70 reaches the preset valve closing pressure, the safety valve 88 is closed to prevent the internal gas from leaking out. At the same time, it also prevents external air from entering the casing 70 and causing adverse effects. Moreover, it can also prevent the precipitated hydrogen from flashing back when exposed to an open flame, thereby detonating the gas inside the casing 70 .

A liquid replenishment port (not shown) for replenishing the aqueous electrolyte 78 may also be provided on the casing 70 . In this way, when the water-based electrolyte 78 is less, the water-based electrolyte 78 can be injected through the liquid replenishment port.

Preferably, the liquid replenishment port is an installation hole (not shown) where the safety valve 88 is installed.

Please refer to Figures 18 and 19, the batteries are stacked. Specifically, the diaphragm 76 is an integral strip structure, and the diaphragm 76 is folded in a Z shape. The positive electrode 72 and the negative electrode 74 are stacked and arranged at the gap of the separator 76 . At this time, the separator 76 is positioned between the positive electrode 72 and the negative electrode 74 to insulate the positive electrode 72 and the negative electrode 74 from each other.

The positive electrode 72 , the separator 76 and the negative electrode 74 are also pressed into a square plate shape. Correspondingly, the casing 70 is also set in a square shape, such as a cuboid or a cube, so that the battery can be designed as a square battery.

Please refer to 20 , the battery is a winding type, and the battery includes a positive electrode 72 , a negative electrode 74 and a separator 76 . The positive electrode 72 , the separator 76 and the negative electrode 74 are wound to form a flat cell, and the separator 76 is located between the positive electrode 72 and the negative electrode 74 . Correspondingly, the casing 70 is also set in a square shape, such as a cuboid or a cube, so that the battery in this embodiment can be designed as a square battery.

Preferably, the positive electrode 72 , the separator 76 and the negative electrode 74 are all arranged in a strip shape. It can be wound into different turns according to the needs.

Specifically, the flat-shaped electric core includes two opposite planes 90, and two arc-shaped portions 92 connected to the two planes 90 and arranged opposite to each other. At least one of the positive winding end 94 and the negative winding end 96 is located at the arc portion 92 of the flat cell.

Preferably, the positive winding termination end 94 and the negative winding termination end 96 are respectively located at the two arc-shaped portions 92 opposite to each other of the flat-shaped electric core.

Preferably, the positive winding end 94 and the negative winding end 96 are located at the same arc portion 92 of the flat cell.

When the battery is being charged and discharged, the thickness of the pole piece will expand, resulting in an increase in the overall thickness of the flat battery cell. However, the positive winding terminal 94 and the negative winding terminal 96 are arranged at the arc portion 92, since there is a space between the arc portion 92 and the casing 70, the space buffers the expansion of the flat-shaped electric core. effect. Therefore, no large stress concentration will be generated at the arc portion 92, thereby avoiding obvious wrinkles at the arc portion 92, and effectively reducing the crystallization of reversible de-intercalation ions.

In Fig. 20, the winding method of the flat cell is as follows: starting from the inner ring, the diaphragm 76 is wound into two layers, and the two layers of diaphragms 76 are attached to each other. According to the design requirements, when the two layers of diaphragms 76 are attached to a certain length Then wind the second circle, starting from the inner circle, followed by two layers of separator 76, negative electrode 74, separator 76 wound to the second circle, positive electrode 72, separator 76 wound to the second circle, and then continue to roll Wind around the negative electrode 74, the diaphragm 76, the positive electrode 72, and the diaphragm 76 to the designed number of turns. Of course, as known to those skilled in the art, there are other winding methods, as long as the positive and negative electrodes are insulated.

The battery provided by the invention has high energy density (up to 60%-80% of lithium ion battery), high power density (expected to reach 200% of lithium ion battery, or even higher), easy to manufacture, completely free of Toxic, environmentally friendly, easy to recycle and low cost (batteries with the same capacity are expected to reach 60% of lead-acid batteries, 20% of lithium-ion batteries, or even lower), and have good cycle performance. In the method, the capacity of the battery remains above 90% after 4000 cycles. Therefore, as a new generation of green energy, the battery in the present invention is very suitable as an energy storage system in the field of large-scale energy storage and as a substitute for lead-acid batteries.

【Pillar structure battery】

The invention also provides a battery, which has a cylindrical structure.

Implementation Mode Nine

A battery. The battery includes a casing, a positive electrode, a negative electrode, a separator and an aqueous electrolyte arranged in the casing, and the separator is arranged between the positive electrode and the negative electrode.

The positive electrode includes a positive electrode current collector and a positive electrode active material that participates in an electrochemical reaction, and the positive electrode active material includes a compound that can reversibly extract and intercalate ions; the negative electrode is selected from metals, alloys, or carbon-based materials; the aqueous electrolyte includes electrolytes, and the electrolytes can at least ionize out Active ions, the active ions are reduced and deposited on the negative electrode during charging to form negative active materials, and the negative active materials are oxidized and dissolved in the aqueous electrolyte during discharge.

The positive electrode current collector, positive electrode active material, negative electrode, aqueous electrolyte, and separator are the same as those in Embodiment 1, and will not be repeated here.

Similarly, the setting of the negative pole is the same as that of Embodiment 1, that is, the negative pole includes a negative electrode current collector, and at this time, the negative pole can only be used as a substrate for electron collection and conduction and does not participate in the electrode reaction; Copper foil and zinc foil, the zinc foil is consistent with the negative electrode active material.

The casing is set in a cylindrical shape, and the positive electrode, the diaphragm, the negative electrode and the casing are arranged coaxially.

Specifically, the positive electrode, the separator and the negative electrode in the battery can be wound to form a cylindrical cell and placed in the casing.

21 and 22, the negative electrode 160 and the separator 156 of the battery 150 are cylindrical, the positive current collector 152 is cylindrical, and the positive active material 158 is disposed between the separator 156 and the positive current collector 152 . The battery 150 also includes a retaining ring 154 that secures the positive current collector 152, the separator 156, the negative electrode 160, and the case (not shown). The material of the fixing ring 154 is polyvinyl chloride, and there are two fixing rings 154, which are respectively arranged at two ends of the casing. The fixing ring 154 includes an upper ring 162 and a lower ring 164. The upper ring 162 and the lower ring 164 are integrally formed. The upper ring 162 fixes the positive current collector 152 and the separator 156, and the lower ring 164 fixes the separator 156 and the negative electrode 160. The outer diameter of the upper layer ring 162 is the same as the inner diameter of the negative electrode 160, and the inner diameter of the upper layer ring 162 is the same as the diameter of the positive electrode current collector 152; of the same diameter.

In the embodiment where the positive electrode current collector 152 is cylindrical, specifically, as shown in FIG. 21 and FIG. 22 : a battery 150 includes a positive electrode current collector 152, a positive electrode active material 158, a separator 156, a negative electrode 160, an aqueous electrolytic Liquid (not shown in the figure), fixed ring 154 and casing; Positive electrode current collector 152 and positive electrode active material 158, diaphragm 156, negative electrode 160 and casing are arranged coaxially; Negative electrode 160 and diaphragm 156 are all cylindrical tubes; Positive electrode The active material 158 is arranged between the positive electrode current collector 152 and the diaphragm 156; the diaphragm 156 is arranged between the positive electrode active material 158 and the negative electrode 160; the negative electrode 160 is arranged between the diaphragm 156 and the casing; the aqueous electrolyte is arranged in the casing; The ring 154 is disposed at one end of the casing, and the fixing ring 154 fixes the positive electrode collector 152 , the diaphragm 156 and the negative electrode 160 ; preferably, the positive electrode collector 152 is a graphite rod.

Specifically, the material of the fixing ring 154 is polyvinyl chloride, and there are two fixing rings 154, which are respectively arranged at two ends of the battery housing, one is arranged at the top of the battery, and the other is arranged at the bottom of the battery. As shown in Figure 22: the fixed ring 154 includes an upper ring 162 and a lower ring 164, the upper ring 162 and the lower ring 164 are integrally formed, the upper ring 162 fixes the positive current collector 152 and the diaphragm 156, and the lower ring 164 fixes the diaphragm 156 and the negative electrode 160. The outer diameter of the upper layer ring 162 is the same as the inner diameter of the negative electrode 160, and the inner diameter of the upper layer ring 162 is the same as the diameter of the positive electrode current collector 152; of the same diameter.

In the embodiment in which the positive electrode current collector is cylindrical, the battery further includes a positive electrode conductive agent, and the positive electrode conductive agent is uniformly mixed with the positive electrode active material 158 and placed between the positive electrode current collector 152 and the separator 156 . Specifically, the cylindrical positive current collector 152, the cylindrical separator 156 and the fixing ring 154 arranged at the bottom of the battery are first assembled, the positive conductive agent, the positive active material 158 and the solvent are mixed uniformly to form a positive slurry, and then the positive electrode The slurry is poured into the gap formed by the separator 156 and the positive electrode collector 152 , and dried, that is, the positive electrode conductive agent and the positive electrode active material 158 are formed between the positive electrode collector 152 and the separator 156 . The positive electrode conductive agent is selected from one or more of conductive polymers, activated carbon, graphene, carbon black, carbon fibers, metal fibers, metal powders, and metal flakes. The solvent is selected from deionized water or ethanol.

In the embodiment in which the positive electrode current collector is cylindrical, the cylindrical negative electrode 160 can be a cylindrical negative electrode current collector, and the cylindrical positive electrode current collector 152, the cylindrical separator 156, and the cylindrical negative electrode After the current collector and the fixing ring arranged at the bottom of the battery are fixed, the negative active material is added between the cylindrical separator 156 and the cylindrical negative current collector; The cylindrical negative electrode 160 is formed after the electroplating or sputtering method is formed on the negative electrode current collector.

The battery provided by the invention has the characteristics of high energy density, high power density, easy manufacture, safety and non-toxicity, environmental protection, easy recycling and low cost, and the battery has good cycle performance. Therefore, the battery in the invention is used as a new A generation of green energy, very suitable as an energy storage system in the field of large-scale energy storage and a substitute for lead-acid batteries.

The units of weight and volume percentage in the present invention are well known to those skilled in the art, for example, volume percentage refers to the weight of solute in 100 ml of solution. Unless otherwise defined, all professional and scientific terms used herein have the same meanings as commonly understood by those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be applied to the method of the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only.

Below in conjunction with embodiment, the content of the present invention is described more specifically. It should be understood that the practice of the present invention is not limited to the following examples.

Example 1

LiMn ₂ O ₄ (Hunan Shanshan, LMO021 type), conductive carbon black (TIMCAL, super P), binder sodium carboxymethyl cellulose (SP Kelco, 30000) and water according to the mass ratio of 90:6: Mix evenly at a ratio of 1:50, add 3 parts of styrene-butadiene rubber emulsion (Korean Daikin), and continue mixing for 10 minutes to make active material slurry. Use an aluminum foil with a length of 80 mm, a width of 60 mm, and a thickness of 20 microns as the positive current collector, and place the aluminum foil between two conductive films with a thickness of 50 microns. The size of the conductive film is slightly larger than that of the aluminum foil. Aluminum foil, and ensure that the part of the conductive film that is more than the aluminum foil is well sealed. The active material slurry is evenly coated on the first and second sides of the composite current collector with a coating density of 700g/m ² , dried at 60°C, and rolled with a pressure of 10 tons on a roller press to obtain positive electrode.

Specifically, the conductive film is a composite material containing polypropylene and conductive carbon black.

The diaphragm is an AGM fiberglass diaphragm with a thickness of 2 mm and a size of 70 x 70 mm. The negative electrode is a 50-micron-thick zinc plate, comparable in size to the separator. The electrolyte is a mixed aqueous solution of 2mol/L ZnSO ₄ and 1mol/L Li ₂ SO ₄ .

The battery is assembled in the following way: the obtained positive electrode is placed between two negative electrodes, and a separator is placed between the positive electrode and the negative electrode. After the assembly is completed, 12 ml of electrolyte is injected, and the charge and discharge test can be started after standing for 3 hours.

Example 2

In Example 2, the positive current collector is copper foil, and the rest of the battery structure and testing methods are the same as in Example 1.

Example 3

In Example 3, the positive electrode current collector is stainless steel foil, and the rest of the battery structure and testing methods are the same as in Example 1.

Example 4

In embodiment 4, the thickness of the conductive film is 100 microns, and the rest of the battery structure and testing method are the same as in embodiment 1.

Battery performance test

The batteries in Examples 1 to 4 were subjected to a charge-discharge cycle test at room temperature. The conditions of the charge-discharge cycle test are: charge to 2.1V at a constant current of 0.25C, stop for 10 minutes, discharge to 1.4V at a constant current of 1C, and stop for 10 minutes, as a cycle.

Fig. 23 is a charge-discharge cycle performance diagram of the battery in Example 1. It can be seen from the figure that the battery can work normally and the performance is very stable after many cycles. Similarly, the batteries in Examples 2 to 4 can work continuously and stably.

Example 5

Mix the positive electrode active material LiMn ₂ O ₄ , the conductive agent acetylene black (AB), and the binder polyvinylidene fluoride (PVDF) in a weight ratio of 80:10:10, and use N-methylpyrrolidone as the solvent to make the positive electrode slurry , coated the positive electrode slurry on one side of the current collector with a thickness of 100 μm, put it into a vacuum drying oven, and dried it at 60° C. for 0.5 h to form a bipolar electrode with a thickness of 400 μm. The current collector is made of conductive plastic, specifically, the conductive plastic is a composite material containing polypropylene and conductive carbon black.

The positive current collector and the negative lead-out electrode are made of stainless steel foil, and one side of the positive current collector is coated with a conductive film with a thickness of 50 μm by hot pressing. The conductive film is a composite film of polyethylene and carbon black. According to the preparation of bipolar In the process of positive electrode, the positive electrode active material is coated with the same thickness on the side of the positive electrode collector coated with the conductive film. The thickness of the positive current collector and the negative lead-out electrode was 2 mm.

The aqueous electrolyte is an aqueous solution containing 1 mol/L lithium sulfate and 2 mol/L zinc sulfate; the diaphragm is made of glass fiber (AGM), the area of the diaphragm is smaller than the area surrounded by the rectangular sealing ring, and the thickness of the diaphragm is 600 μm; the sealing part is made of high It is a rectangular sealing ring of 1 mm, and the area of the rectangular sealing ring is slightly smaller than the area of the lead-out electrode and the current collector.

Laminate a rectangular sealing ring on the negative lead-out electrode, and then place a separator soaked in an aqueous electrolyte in the ring of the seal ring, and then stack a bipolar electrode and a positive lead-out electrode in sequence, and the bipolar electrode and the positive lead-out electrode are coated with positive active materials. One side is placed facing the negative lead-out electrode, and the sealing ring is used to seal the water-based electrolyte disposed between the positive lead-out electrode and the adjacent bipolar electrode and between the bipolar electrode and the adjacent negative lead-out electrode.

Battery performance test

The battery in Example 5 was subjected to a charge-discharge cycle test at room temperature. The conditions of the charge-discharge cycle test are: charge to 4.2V at a constant current of 1C, stop for 10 minutes, discharge to 2.8V at a constant current of 1C, and stop for 10 minutes, as a cycle.

Example 6

In Example 6, the number of bipolar electrodes is three, and the rest of the battery structure and preparation method are the same as in Example 5.

Battery performance test

The battery in Example 6 was subjected to a charge-discharge cycle test at room temperature. The conditions of the charge-discharge cycle test are: charge to 8.4V at a constant current of 1C, stop for 10 minutes, discharge to 5.6V at a constant current of 1C, and stop for 10 minutes, as a cycle.

Example 7

In Example 7, the number of bipolar electrodes is 5, and the rest of the structure and preparation method of the battery are the same as in Example 5.

Battery performance test

The battery in Example 7 was subjected to a charge-discharge cycle test at room temperature. The conditions of the charge-discharge cycle test are: charge to 12.6V at a constant current of 1C, stop for 10 minutes, discharge to 8.4V at a constant current of 1C, and stop for 10 minutes, as a cycle.

Example 8

In Example 8, the current collector of the bipolar electrode is made of stainless steel with a thickness of 50 μm, and the rest of the battery composition, preparation method and battery performance test are the same as in Example 5.

Example 9

In Example 9, one side of the positive current collector is not coated with a conductive film, and the rest of the battery composition, preparation method and battery performance test are the same as in Example 5.

Table 1 shows the battery performance of the batteries in Examples 5 to 9 charged and discharged at a rate of 1C, and charged and discharged 100 times:

Table 1

Example 10

Mix the positive electrode active material LiMn ₂ O ₄ , super-p carbon black, and the binder PVDF according to the weight ratio of 8:1:1, and use NMP as the solvent to prepare the positive electrode slurry, which is evenly coated on the positive electrode assembly with a thickness of 80 μm. Fluid graphite foil, followed by drying and pressing to obtain the positive electrode; the negative electrode includes zinc foil and graphite foil with a thickness of 50 μm, and metal zinc is plated on the graphite foil as the negative electrode active material; the separator is glass felt cloth.

The obtained positive electrode, diaphragm, and negative electrode are wound to form a cylindrical battery cell, which is placed in a cylindrical shell; the electrolyte added to the battery is an aqueous solution containing 2mol/L lithium acetate and 1.5mol/L zinc acetate. A 0.1 mol/L LiOH solution was added dropwise to the electrolyte to adjust the pH of the electrolyte to 4. At room temperature, after standing for 12 hours, the battery was charged and discharged with a current of 100mA, and the voltage range was 1.5-2.35V.

Example 11

A battery was manufactured in the same manner as in Example 10, except that the graphite foil in the negative electrode of Example 10 was replaced by passivated 316 stainless steel.

Example 12

A battery was fabricated in the same manner as in Example 10, except that the graphite foil in the negative electrode of Example 10 was replaced with copper foil.

Example 13

A battery, the positive current collector is a graphite rod with a diameter of 4 mm and a length of 62 mm; the material of the diaphragm is non-woven fabric, the diaphragm is cylindrical, the outer diameter of the diaphragm is 11 mm, the inner diameter of the diaphragm is 10 mm, and the length of the diaphragm is 58mm; the negative electrode includes copper foil and zinc, and the zinc is formed on the copper foil by sputtering to obtain a cylindrical negative electrode. The outer diameter of the negative electrode is 17mm, the inner diameter of the negative electrode is 16mm, and the length of the negative electrode is 58mm. Thick copper tab leads out to the battery; the material of the housing is polyvinyl chloride (PVC), the inner diameter of the housing is 17mm, the outer diameter of the housing is 18mm, and the length of the housing is 60mm; the material of the fixing ring is PVC Vinyl (PVC), there are two fixing rings, which are respectively set at both ends of the battery. The first fixing ring is placed on the top of the battery, and the second fixing ring is placed at the bottom of the battery. The ring and the lower ring are integrally formed, the inner diameter of the upper ring is 4mm, the outer diameter of the upper ring is 10mm, the thickness of the upper ring is 3mm, the inner diameter of the lower ring is 4mm, the outer diameter of the lower ring is 16mm, and the thickness of the lower ring is 1mm.

The assembly process of the specific battery is as follows: LiMn ₂ O ₄ is used as the positive electrode active material, and the positive electrode active material, the conductive agent Super-P, are mixed in deionized water according to the weight ratio of 90:10, and the positive electrode slurry is obtained by mixing evenly; After assembling the diaphragm, the second fixing ring and the graphite rod, pour the positive electrode slurry into the gap formed by the diaphragm and the graphite rod, and pour 10 g of the positive electrode slurry into it, and dry it at 80°C to obtain the positive electrode, the positive electrode in the diaphragm The mixture of the active material and the conductive agent is 5g; the cylindrical negative pole is set outside the cylindrical diaphragm, and the cylindrical shell is arranged outside the cylindrical negative pole; the electrolyte is 544g zinc chloride and 21g anhydrous lithium chloride, Dissolve it in 600g deionized water, then titrate 0.1mol/L lithium hydroxide in the electrolyte to adjust the pH value of the electrolyte to 4.3, then use deionized water to set the volume to 1L, and add 5g of the lithium hydroxide to the battery of this embodiment. electrolyte. After assembling the separator, second fixing ring, graphite rod, positive electrode, negative electrode, shell and electrolyte, let it stand for 12 hours, and then start charging and discharging with a current of 100mA, and the charging and discharging voltage range is 1.5-2.35V.

Example 14

A battery, the positive current collector is a graphite rod with a diameter of 4 mm and a length of 62 mm; the material of the diaphragm is non-woven fabric, the diaphragm is cylindrical, the outer diameter of the diaphragm 3 is 11 mm, the inner diameter of the diaphragm is 10 mm, and the length of the diaphragm is The negative electrode includes copper foil and zinc, the outer diameter of the negative electrode is 17mm, the inner diameter of the negative electrode is 16mm, and the length of the negative electrode is 58mm. There is a copper tab with a thickness of 0.1mm on the negative electrode to lead out the battery; the material of the shell is poly Vinyl chloride (PVC), the inner diameter of the casing is 17mm, the outer diameter of the casing is 18mm, and the length of the casing is 60mm; the material of the fixing ring is polyvinyl chloride (PVC), and there are two fixing rings, which are respectively set on the battery At both ends of the battery, the first fixing ring is placed on the top of the battery, and the second fixing ring is placed on the bottom of the battery. The fixing ring includes an upper ring and a lower ring. The upper ring and the lower ring are integrally formed. The inner diameter of the upper ring is 4mm. The outer diameter of the upper ring is 10mm, the thickness of the upper ring is 3mm, the inner diameter of the lower ring is 4mm, the outer diameter of the lower ring is 16mm, and the thickness of the lower ring is 1mm.

The specific battery assembly process is as follows: LiMn ₂ O ₄ is used as the positive electrode active material, the positive electrode active material 22, the conductive agent Super-P, and the weight ratio of 90:10 are mixed in deionized water, and the positive electrode slurry is obtained by mixing evenly; After assembling the separator, the second fixing ring and the graphite rod, pour the positive electrode slurry into the separator, the amount of pouring the positive electrode slurry is 12g, and dry at 80°C to obtain the positive electrode, the positive electrode active material and the conductive agent in the separator The mixture is 6g; after the cylindrical copper foil and graphite rod, the cylindrical diaphragm and the second fixing ring are fixed, zinc is added between the cylindrical diaphragm and the cylindrical copper foil Obtain cylindrical cylindrical negative pole; Electrolyte is 544g zinc chloride and 21g anhydrous lithium chloride, dissolves in 600g deionized water, then titrates 0.1mol/L lithium hydroxide in electrolytic solution to adjust the pH value of electrolytic solution to 4.3 , and then dilute it to 1 L with deionized water, and add 6 g of the electrolyte to the battery of this embodiment. After assembling the diaphragm, the second fixing ring, the graphite rod, the positive electrode, the negative electrode, the casing and the electrolyte, let it stand for 12 hours, and then start charging and discharging with a current of 100mA, and the charging and discharging voltage range is 1.5-2.35V.

Example 15

A battery was fabricated in the same manner as in Example 13, except that graphite foil was used instead of copper foil in the negative electrode.

The batteries provided in Examples 10 to 15 have good cycle performance.

Although the inventor has described and listed the technical solutions of the present invention in more detail, it should be understood that it is obvious for those skilled in the art to make modifications and/or modifications to the above embodiments or to adopt equivalent alternatives. It cannot deviate from the essence of the spirit of the present invention, and the terms appearing in the present invention are used to illustrate and understand the technical solution of the present invention, and shall not constitute a limitation of the present invention.

Claims (19)

1. a kind of battery, including housing, is arranged at positive pole, two negative poles, aqueous electrolyte and barrier films in the housing,

The positive pole includes composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body and is coated on Conducting film on the plus plate current-collecting body, the material of the conducting film includes polymer and conductive filler, and the polymer is accounted for leads The weight proportion of electrolemma is 50-95%, and the composite current collector has the first face and the second face being oppositely arranged, and the positive pole is lived Property material is arranged on first face and the second face, the positive active material can it is reversible deviate from-embedded ion；

The negative pole is selected from metal, alloy or carbon-based material；

The aqueous electrolyte includes electrolyte, and the electrolyte can at least ionize out active ion, and the active ion exists It is reduced during charging and is deposited on the negative pole formation negative electrode active material, the negative electrode active material is oxidized dissolving in electric discharge In the aqueous electrolyte；

The barrier film keeps the aqueous electrolyte；

The positive pole and negative pole stacking are arranged in the housing, and the positive pole is placed between described two negative poles, described two Negative pole shares the positive pole, and the barrier film is located between the positive pole and negative pole.

2. a kind of battery, including housing, is arranged at two positive poles, negative pole, aqueous electrolyte and barrier films in the housing,

The positive pole includes composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body and is coated on Conducting film on the plus plate current-collecting body, the material of the conducting film includes polymer and conductive filler, and the polymer is accounted for leads The weight proportion of electrolemma is 50-95%, and the composite current collector has the first face and the second face being oppositely arranged, first face It is relative with the negative pole, the positive active material is provided with least described first face, the positive active material can Inverse abjection-embedded ion；

The negative pole is selected from metal, alloy or carbon-based material；

The aqueous electrolyte includes electrolyte, and the electrolyte can at least ionize out active ion, and the active ion exists It is reduced during charging and is deposited on the negative pole formation negative electrode active material, the negative electrode active material is oxidized dissolving in electric discharge In the aqueous electrolyte；

The barrier film keeps the aqueous electrolyte；

The positive pole and negative pole stacking are arranged in the housing, and the negative pole is placed between described two positive poles, described two Positive pole shares the negative pole, and the barrier film is located between the positive pole and negative pole.

3. a kind of battery, including housing, is arranged at positive pole in the housing, negative pole, aqueous electrolyte and barrier film,

The positive pole includes composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body and is coated on Conducting film on the plus plate current-collecting body, the material of the conducting film includes polymer and conductive filler, and the polymer is accounted for leads The weight proportion of electrolemma is 50-95%, and the composite current collector has the two sides being oppositely arranged, wherein, at least described Composite Set Be provided with positive active material in the fluid one side relative with the negative pole, the positive active material can it is reversible deviate from-it is embedding Enter ion；

The battery includes n to the positive pole and negative pole, and n >=2, two adjacent positive poles share negative between two positive poles Pole, two adjacent negative poles share the positive pole between two negative poles；

The negative pole is selected from metal, alloy or carbon-based material；

The aqueous electrolyte includes electrolyte, and the electrolyte can at least ionize out active ion, and the active ion exists It is reduced during charging and is deposited on the negative pole formation negative electrode active material, the negative electrode active material is oxidized dissolving in electric discharge In the aqueous electrolyte；

The barrier film keeps the aqueous electrolyte；

In the housing, the barrier film is located between the positive pole and negative pole the alternate stacked arrangement of the positive pole, negative pole.

4. the battery according to any one in claim 1-3, it is characterised in that：The housing is square.

5. battery according to claim 4, it is characterised in that：The positive pole, barrier film and negative pole form tabular.

6. battery according to claim 5, it is characterised in that：The positive pole, barrier film and negative pole winding shaping.

7. the battery according to any one in claim 1-3, it is characterised in that：The housing is cylinder barrel shaped, described Positive pole, the barrier film, the negative pole and the housing arranged in co-axial alignment.

8. battery according to claim 7, it is characterised in that：The positive pole, barrier film and negative pole form cylinder by winding Shape is arranged in the housing.

9. the battery according to any one in claim 1-3, it is characterised in that：The polymer is selected from polyethylene, gathers Propylene, polybutene, polyvinyl chloride, polystyrene, polyamide, makrolon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, Polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.

10. the battery according to any one in claim 1-3, it is characterised in that：The conductive filler is selected from conductive poly- Compound, carbon-based material or metal oxide.

11. battery according to any one in claim 1-3, it is characterised in that：The material of the conducting film is selected from and leads Electric polymer.

12. battery according to any one in claim 1-3, it is characterised in that：The housing is set to aluminum plastic film.

13. battery according to any one in claim 1-3, it is characterised in that：The housing is provided with fluid infusion, institute Fluid infusion is stated for supplementing the aqueous electrolyte.

14. battery according to any one in claim 1-3, it is characterised in that：The battery is also included for controlling The safety valve of pressure in the housing.

15. battery according to any one in claim 1-3, it is characterised in that：The positive active material has point Spinel structure, layer structure or olivine structural.

16. battery according to any one in claim 1-3, it is characterised in that：The material choosing of the plus plate current-collecting body One kind from vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or by the one kind in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloys, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-Rh alloys or by the one kind in the above-mentioned alloy of Passivation Treatment.

17. battery according to any one in claim 1-3, it is characterised in that：The material of the negative pole is selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or by least one in the metal of Passivation Treatment, or contain above-mentioned metal At least one at least one in alloy, or graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is tin plating, or yellow Copper.

18. battery according to any one in claim 1-3, it is characterised in that：The active ion include metal from Son, metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.

19. battery according to any one in claim 1-3, it is characterised in that：The active ion is with hydrochloride, sulphur At least one form in hydrochlorate, acetate, nitrate or formates is present in the aqueous electrolyte.