CN112436107B - Battery based on metal electrode - Google Patents

Battery based on metal electrode Download PDF

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Publication number
CN112436107B
CN112436107B CN201910788166.7A CN201910788166A CN112436107B CN 112436107 B CN112436107 B CN 112436107B CN 201910788166 A CN201910788166 A CN 201910788166A CN 112436107 B CN112436107 B CN 112436107B
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metal
positive electrode
electrode
dendrite
negative electrode
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CN112436107A (en
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李长明
辛民昌
吴超
辛程勋
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Qingdao Jiuhuan Xinyue New Energy Technology Co ltd
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Qingdao Jiuhuan Xinyue New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

The invention discloses a battery based on a metal electrode, which comprises a positive electrode, a negative electrode and an electrolyte; the positive electrode includes a positive electrode active material; the positive electrode active material is prepared by mixing a metal material and a positive electrode material for adjusting potential, or the positive electrode active material is prepared by compounding the metal material and at least one layer of positive electrode material for adjusting potential; the negative electrode includes a negative electrode active material; the negative active material is made of a metal material; or, the negative active material is made of a mixture of a metal material and a negative material for adjusting potential; or the negative electrode active material is formed by compounding a metal material and at least one layer of negative electrode material for adjusting potential. The invention also discloses a laminated battery based on the all-metal electrode. According to the battery based on the metal electrode, the positive electrode active material and the negative electrode active material are both mainly made of metal materials, so that the capacity and the energy density of the battery can be effectively improved.

Description

Battery based on metal electrode
Technical Field
The invention belongs to the technical field of energy storage equipment, and particularly relates to a battery based on a metal electrode.
Background
A "lithium battery" is a type of battery using a nonaqueous electrolyte solution with lithium metal or a lithium alloy as a negative electrode material. Lithium metal batteries were first proposed and studied by Gilbert n.lewis in 1912. In the 70 s of the 20 th century, m.s.whitetingham proposed and began to study lithium ion batteries. Because the chemical characteristics of lithium metal are very active, the lithium metal has very high requirements on the environment in processing, storage and use. With the development of science and technology, lithium batteries have become the mainstream nowadays.
Lithium batteries can be broadly classified into two types: lithium metal batteries and lithium ion batteries. Lithium ion batteries do not contain lithium in the metallic state and are rechargeable. The fifth generation of rechargeable batteries, lithium metal batteries, was born in 1996, and the safety, specific capacity, self-discharge rate and cost performance of rechargeable batteries were all superior to those of lithium ion batteries. Due to its own high technical demand restrictions, only a few national companies are producing such lithium metal batteries.
In general, a lithium metal battery uses manganese dioxide as a positive electrode material, lithium metal or an alloy metal thereof as a negative electrode material, and a nonaqueous electrolyte solution.
Discharging reaction: li + MnO 2 ＝LiMnO 2
In general, a lithium ion battery uses a lithium alloy metal oxide as a positive electrode material, graphite as a negative electrode material, and a nonaqueous electrolyte.
The reaction occurring at the charged positive electrode is
LiCoO 2 ＝＝Li (1-x) CoO 2 +XLi++Xe - (electronic)
The reaction occurring at the charged negative electrode is
6C+XLi++Xe - ＝LixC 6
Overall reaction of the rechargeable battery: liCoO 2 +6C＝Li (1-x) CoO 2 +Li x C 6
The existing lithium metal battery and lithium ion battery also have the problems of low capacity and low energy density.
Disclosure of Invention
In view of the above, the present invention provides a battery based on metal electrodes, wherein the positive electrode and the negative electrode are both made of metal materials, so as to effectively improve the battery capacity and energy density.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention firstly provides a battery based on a metal electrode, which comprises a positive electrode, a negative electrode and an electrolyte;
the positive electrode includes a positive electrode active material;
the positive electrode active material is prepared by mixing a metal material and a positive electrode material for adjusting potential, or the positive electrode active material is prepared by compounding the metal material and at least one layer of positive electrode material for adjusting potential;
the anode includes an anode active material;
the negative electrode active material is made of a metal material; or the like, or, alternatively,
the negative electrode active material is made of a mixture of a metal material and a negative electrode material for adjusting potential; or the like, or a combination thereof,
the negative electrode active material is formed by compounding a metal material and at least one layer of negative electrode material for adjusting potential.
Further, the metal material is made of one or an alloy of at least two of metal lithium, metal magnesium, metal aluminum, metal sodium and metal potassium.
Further, the positive electrode materials include, but are not limited to, iron phosphate, lithium cobaltate, manganese phosphate, ternary positive electrode materials (532, 622, and 811), polysulfide, and metal air positive electrode materials.
Further, the mass ratio of the positive electrode material to the metal material in the positive electrode active material is 5% to 80%.
Further, a dendrite inhibiting material I for inhibiting growth of dendrites is arranged in the positive electrode active material, and the dendrite inhibiting material I comprises but is not limited to at least one of metal tin, metal titanium, metal tungsten, metal lead, metal aluminum and quaternary ammonium salt.
Further, the mass ratio of the dendrite inhibiting material I to the metal material in the positive electrode active material is 1-100%.
Further, the negative electrode material includes, but is not limited to, silicon oxide and derivatives thereof, graphene and derivatives thereof, carbon nanotubes and derivatives thereof, biomass carbon materials and derivatives thereof, lithium-containing polymers and derivatives thereof, and surface-functionalized carbon materials.
Further, the mass ratio of the negative electrode material to the metal material in the negative electrode active material is 0.01% to 80%.
Further, a dendrite inhibiting material II for inhibiting the growth of dendrites is arranged in the negative active material, and the dendrite inhibiting material II comprises at least one of metal tin, metal titanium, metal tungsten, metal lead, metal aluminum and quaternary ammonium salt.
Further, the mass ratio of the dendrite inhibiting material II to the metal material of the negative electrode active material is 1-100%.
Further, the electrolyte includes an electrolytic solution and a separator provided between the positive electrode and the negative electrode for ionic conduction.
Further, a dendrite inhibiting layer I for inhibiting growth of dendrites and conducting ions is arranged between the positive electrode and the diaphragm, and/or,
and a dendrite inhibiting layer II which is used for inhibiting dendrite growth and can conduct ions is arranged between the negative electrode and the diaphragm.
Further, the dendrite inhibiting layer I is compounded on the positive electrode, or the dendrite inhibiting layer I is compounded on the diaphragm;
the dendrite inhibiting layer II is compounded on the negative electrode, or the dendrite inhibiting layer II is compounded on the diaphragm.
Furthermore, the dendritic crystal inhibition layer I and the dendritic crystal inhibition layer II are both made of composite materials for inhibiting dendritic crystal growth, and the composite materials are made of functional metal materials for inhibiting dendritic crystal growth and ion transmission materials for realizing ion conduction in a mixing mode;
the functional metal material is at least one of metal tin, metal titanium, metal tungsten, metal lead and metal aluminum;
the ion conducting material adopts at least one of metal salt, quaternary ammonium salt and ion conductor material.
Further, the electrolyte adopts a solid ion conductor.
Further, a dendrite inhibiting layer III for inhibiting dendrite growth and enabling ionic conduction is arranged between the positive electrode and the solid ion conductor, and/or,
and a dendrite inhibiting layer IV which is used for inhibiting dendrite growth and can be conducted by ions is arranged between the negative electrode and the solid ion conductor.
Further, the dendrite inhibiting layer III is compounded on the positive electrode, or the dendrite inhibiting layer III is compounded on the solid ion conductor;
and the dendritic crystal inhibition layer IV is compounded on the negative electrode, or the dendritic crystal inhibition layer IV is compounded on the solid ion conductor.
Furthermore, the dendritic crystal inhibition layer III and the dendritic crystal inhibition layer IV are both made of a composite material for inhibiting dendritic crystal growth, and the composite material is made of a functional metal material for inhibiting dendritic crystal growth and an ion transmission material for realizing ion conduction in a mixing manner;
the functional metal material adopts at least one of metal tin, metal titanium, metal tungsten, metal lead and metal aluminum;
the ion conducting material adopts at least one of metal salt, quaternary ammonium salt and ion conductor material.
The invention also provides a laminated battery based on the all-metal electrode;
comprising at least two cells of any one of claims 1-18 laminated together;
in two adjacent batteries, the positive electrode of one battery and the negative electrode of the other battery are adjacently arranged, and a bipolar current collecting plate which is electrically conductive and ion-isolated is arranged between the adjacent positive electrode and the adjacent negative electrode; or the like, or, alternatively,
and in two adjacent batteries, the positive electrode of one battery and the positive electrode of the other battery are adjacently arranged, or the negative electrode of one battery and the negative electrode of the other battery are adjacently arranged, and an electronically conductive and ion-isolated bipolar current collecting plate is arranged between the two adjacent positive electrodes or the two adjacent negative electrodes.
The invention has the beneficial effects that:
the battery based on the metal electrode is characterized in that the positive electrode active material is made of a mixture of a metal material and a positive electrode material for adjusting the potential or is compounded with the positive electrode material for adjusting the potential on the metal material, so that a potential difference is formed between the positive electrode and the negative electrode; certainly, the negative electrode active material does not need to be provided with a negative electrode material, or the negative electrode material can be mixed in the metal material of the negative electrode or compounded on the metal material of the negative electrode, so that the potential of the negative electrode is reduced, and the potential difference between the positive electrode and the negative electrode is further improved; when the lithium ion battery is used for the first time, the battery needs to be charged firstly, so that the metal material of the positive electrode is changed into metal ions, and the technical effect of charge-discharge cycle can be met; in summary, the positive electrode active material and the negative electrode active material are both made of metal materials, and the battery capacity and the energy density can be effectively improved by utilizing the characteristic of high metal capacity.
The dendritic crystal inhibiting material I is arranged in the metal material of the anode, or when the electrolyte is electrolyte, the dendritic crystal inhibiting layer I is arranged between the anode and the diaphragm, or when the electrolyte adopts a solid ion conductor, the dendritic crystal inhibiting layer III is arranged between the anode and the solid ion conductor, so that the growth of the dendritic crystal on the anode can be effectively inhibited, the safety performance of the battery is improved, and the cycle service life of the battery is prolonged;
similarly, through set up dendrite suppression material II in the metal material of negative pole, or when the electrolyte was electrolyte, set up dendrite suppression layer II between negative pole and diaphragm, or when the electrolyte adopted solid ion conductor, set up dendrite suppression layer IV between negative pole and solid ion conductor, can effectively restrain the dendrite growth on the negative pole, improve battery security performance and cycle life.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
figure 1 is a schematic diagram of the structure of a metal electrode-based battery of embodiment 1 of the present invention,
fig. 2 is a microscopic enlarged view of a positive electrode active material made of a mixture of a metal material and a positive electrode material for adjusting potential;
fig. 3 is a schematic structural diagram of a positive electrode when a positive electrode material layer is disposed between a metal material layer and a positive electrode current collector;
fig. 4 is a schematic structural diagram of the positive electrode when the positive electrode material layer is arranged on the side surface of the metal material layer opposite to the positive electrode current collector;
FIG. 5 is a schematic structural diagram of a positive electrode when a positive electrode material layer is arranged in a metal material layer;
fig. 6 is a schematic structural view when a negative active material is made of a mixture of a metal material and a negative electrode material for adjusting potential;
fig. 7 is a schematic structural view of the negative electrode when the negative electrode material layer is disposed between the metal material layer and the negative electrode current collector;
fig. 8 is a schematic structural view of the negative electrode when the negative electrode material layer is disposed on the side of the metal material layer facing away from the negative electrode current collector;
fig. 9 is a schematic structural diagram of a negative electrode when a negative electrode material layer can also be arranged in the metal material layer;
FIG. 10 is a schematic structural view of a metal electrode-based battery according to example 2 of the present invention;
FIG. 11 is a schematic structural diagram of a dendrite inhibiting layer I on a positive electrode and a dendrite inhibiting layer II on a negative electrode;
FIG. 12 is a schematic structural view of a dendrite inhibiting layer I and a dendrite inhibiting layer II which are compounded on a diaphragm;
FIG. 13 is a schematic view of the structure of example 3 of the metal electrode-based battery of the present invention;
FIG. 14 is a schematic structural diagram of a dendrite inhibiting layer III on a positive electrode and a dendrite inhibiting layer IV on a negative electrode;
FIG. 15 is a schematic structural view of a dendrite suppression layer III being composited on a solid ion conductor and a dendrite suppression layer IV being composited on the solid ion conductor;
fig. 16 is a schematic structural diagram of a laminated cell based on all-metal electrodes, in particular a schematic structural diagram when all cells are connected in series;
fig. 17 is a schematic view of the structure in which all the cells are connected in parallel.
Description of reference numerals:
10-positive electrode; 10 a-a metallic material; 10 b-a positive electrode material; 11-a layer of metallic material; 12-a layer of positive electrode material; 13-positive current collector;
20-negative electrode; 20 a-a metallic material; 20 b-negative electrode material; 21-a layer of metallic material; 22-a layer of anode material; 23-a negative current collector;
30-a membrane; 131-dendrite inhibiting layer I; 132-dendrite suppression layer II 132;
40-a solid-state ion conductor; 141-dendrite-inhibiting layer III; 142-dendrite suppression layer IV;
50-bipolar collector plate;
60-battery.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
Fig. 1 is a schematic structural diagram of a metal electrode-based battery of example 1 of the present invention. The battery of the present embodiment based on a metal electrode includes a positive electrode 10, a negative electrode 20, and an electrolyte between the positive electrode 10 and the negative electrode 20.
The positive electrode 10 includes a positive electrode active material; the positive active material is prepared by mixing a metal material and a positive material for adjusting potential, or the positive active material is formed by compounding the metal material and at least one layer of the positive material for adjusting potential.
Specifically, as shown in fig. 2, a microscopic enlarged view of the positive electrode active material made of a mixture of a metal material and a positive electrode material for adjusting the potential;
as shown in fig. 3-5, which is a schematic structural view of the positive active material formed by combining a metal material 10a and at least one layer of positive material 10b for adjusting the potential, specifically, as shown in fig. 3, the positive material layer 12 may be disposed between the metal material layer 11 and the positive current collector 13; as shown in fig. 4, the positive electrode material layer 12 may also be disposed on the side of the metal material layer 11 facing away from the positive electrode current collector 13; as shown in fig. 5, the positive electrode material layer 12 may also be provided within the metal material layer 11. Of course, the positive electrode material layer 11 may also be provided with at least two layers, and the position where the positive electrode material layer 11 is provided may refer to the position shown in fig. 3 to 5, which will not be described in detail.
The anode 20 includes an anode active material;
the negative active material is made of a metal material, or,
the negative electrode active material is made of a mixture of a metal material 20a and a negative electrode material for potential adjustment 20b, and is a microscopic enlarged view of the case where the negative electrode active material is made of a mixture of a metal material and a negative electrode material for potential adjustment, as shown in fig. 6; or the like, or, alternatively,
the negative active material is formed by compounding a metal material and at least one layer of negative material for adjusting potential. As shown in fig. 7 to 9, which are schematic structural diagrams when the negative active material is formed by combining a metal material and at least one layer of negative material for adjusting potential, specifically, as shown in fig. 7, the negative material layer 22 may be disposed between the metal material layer 21 and the negative current collector 23; as shown in fig. 8, the anode material layer 22 may also be provided on the side of the metal material layer 21 facing away from the anode current collector 23; as shown in fig. 9, the anode material layer 22 may also be provided within the metal material layer 21. Of course, the anode material layer 21 may be provided with at least two layers, and the arrangement position of the anode material layer 21 may refer to the arrangement positions shown in fig. 7 to 9, which will not be described in detail.
Preferably, the metal material 11 is made of, but not limited to, one or an alloy of at least two of metal lithium, metal magnesium, metal aluminum, metal sodium and metal potassium; the metal material in the positive electrode 10 and the metal material in the negative electrode 20 of the present embodiment are the same metal material, and the metal material in the positive electrode 10 and the metal material in the negative electrode 20 of the present embodiment are both metal lithium, which has an advantage of high energy density.
Further, the positive electrode material includes, but is not limited to, iron phosphate, lithium cobaltate, manganese phosphate, ternary positive electrode materials (model numbers include 532, 622, 811, and the like), polysulfide, and a metal air positive electrode material, and the positive electrode material of this embodiment employs lithium iron phosphate. The mass ratio of the positive electrode material to the metal material in the positive electrode active material is 5% to 80%, and under the condition of increasing the potential of the positive electrode 10, the capacity of the positive electrode 10 is not greatly affected.
Further, in order to suppress the growth of dendrites, the present embodiment provides a dendrite suppressing material i for suppressing the growth of dendrites in the positive electrode active material, and the dendrite suppressing material i includes, but is not limited to, at least one of metallic tin, metallic titanium, metallic tungsten, metallic lead, metallic aluminum, and quaternary ammonium salt. The mass ratio of the dendrite inhibiting material i to the metal material in the positive electrode active material of the present embodiment is 1% to 100%.
Further, the negative electrode material includes, but is not limited to, silicon oxide and its derivatives, graphene and its derivatives, carbon nanotubes and its derivatives, biomass carbon materials and its derivatives, lithium-containing polymers and its derivatives, and surface-functionalized carbon materials (e.g., super p, ketjen black, carbon black, etc.), and graphene and its derivatives are used as the negative electrode material of this embodiment. The mass ratio of the negative electrode material to the metal material in the negative electrode active material is 0.01-80%, and under the condition of reducing the potential of the negative electrode 20, the capacity of the negative electrode 20 is not greatly influenced.
Further, a dendrite inhibiting material II for inhibiting the growth of dendrites is provided in the negative active material, and the dendrite inhibiting material II includes, but is not limited to, at least one of metallic tin, metallic titanium, metallic tungsten, metallic lead, metallic aluminum, and quaternary ammonium salt. The mass ratio of the dendrite inhibiting material ii to the metal material in the negative electrode active material of the present embodiment is 1% to 100%.
In the battery based on the metal electrode, the positive electrode active material is made of a mixture of a metal material and a positive electrode material for adjusting the potential or is compounded with the positive electrode material for adjusting the potential, so that a potential difference is formed between the positive electrode and the negative electrode; certainly, the negative electrode active material does not need to be provided with a negative electrode material, or the negative electrode material can be mixed in the metal material of the negative electrode or compounded on the metal material of the negative electrode, so that the potential of the negative electrode is reduced, and the potential difference between the positive electrode and the negative electrode is further improved; when the lithium ion battery is used for the first time, the battery needs to be charged firstly, so that the metal material of the positive electrode is changed into metal ions, and the technical effect of charge-discharge cycle can be met; in summary, the positive electrode active material and the negative electrode active material are both made of metal materials, and the battery capacity and the energy density can be effectively improved by utilizing the characteristic of high metal capacity.
Example 2
Fig. 10 is a schematic structural view of example 2 of the metal electrode-based battery of the present invention. The battery based on the metal electrode of the present embodiment includes a positive electrode 10, a negative electrode 20, and an electrolyte between the positive electrode 10 and the negative electrode 20.
The positive electrode 10 includes a positive electrode active material; the positive active material is prepared by mixing a metal material and a positive material for adjusting potential, or the positive active material is formed by compounding the metal material and at least one layer of the positive material for adjusting potential.
The anode 20 includes an anode active material; the negative electrode active material is made of a metal material, or the negative electrode active material is made of a mixture of a metal material 20a and a negative electrode material 20b for adjusting potential; or the negative active material is formed by compounding a metal material and at least one layer of negative material for adjusting potential.
The electrolyte of the present embodiment includes an electrolytic solution and a separator 30 provided between the cathode 10 and the anode 20 for electronic insulation but ionic conduction. Specifically, a dendrite suppression layer i 131 for suppressing dendrite growth and enabling ionic conduction is provided between the positive electrode 10 and the separator 30, and/or a dendrite suppression layer ii 132 for suppressing dendrite growth and enabling ionic conduction is provided between the negative electrode 20 and the separator 30. In the present embodiment, a dendrite suppression layer i 131 for suppressing dendrite growth and enabling ionic conduction is provided between the positive electrode 10 and the separator 30, and a dendrite suppression layer ii 132 for suppressing dendrite growth and enabling ionic conduction is provided between the negative electrode 20 and the separator 30.
Specifically, a dendrite inhibiting layer I131 is compounded on the positive electrode 10, or the dendrite inhibiting layer I131 is compounded on the diaphragm 30; the dendrite inhibiting layer II 132 is compounded on the negative electrode 20, or the dendrite inhibiting layer II 132 is compounded on the separator 30.
As shown in fig. 11, it is a schematic structural diagram of the case where the dendrite inhibiting layer i 131 is compounded on the positive electrode 10 and the dendrite inhibiting layer ii 132 is compounded on the negative electrode 20;
as shown in fig. 12, a schematic view of a structure in which a dendrite suppression layer i 131 is combined with a separator 30 and a dendrite suppression layer ii 132 is combined with the separator 30 is shown.
Of course, when the dendrite suppression layer i 131 is combined with the positive electrode 10, the dendrite suppression layer ii 132 may be combined with the separator 30, or when the dendrite suppression layer i 131 is combined with the separator 30, the dendrite suppression layer ii 132 may be combined with the negative electrode 20, which will not be described again.
Furthermore, the dendritic crystal inhibition layer I131 and the dendritic crystal inhibition layer II 132 are both made of composite materials for inhibiting dendritic crystal growth, and the composite materials comprise functional metal materials for inhibiting dendritic crystal growth and ion conduction materials for realizing ion conduction;
the functional metal material and the ion conducting material are mixed together by a physical method or a chemical method;
the functional metal material adopts at least one of metal tin, metal titanium, metal tungsten, metal lead and metal aluminum;
the ion conducting material is at least one of metal salt, quaternary ammonium salt and ion conductor material.
Specifically, the metal salt is at least one of, but not limited to, a lithium salt, a sodium salt, and a potassium salt. When the metal salt is selected, the metal salt can be selected to be the same as the metal ion in the battery, for example, the metal salt in the lithium battery can be selected to be a lithium salt, which will not be described again. The ion guide material is made of one or a mixture of at least two of gel, oxide, sulfide and organic polymer.
Specifically, the mass ratio of the functional metal material in the composite material is 0.01-50%, so that the requirement of dendritic crystal growth inhibition can be met, ion conduction cannot be influenced, and the battery performance cannot be influenced.
Further, the composite material of the present embodiment is made into a gel.
The ion conductor material adopts quaternary ammonium salt and/or colloidal ion guide material; or the like, or, alternatively,
the ion conductor material adopts a mixture of metal salt and quaternary ammonium salt; or the like, or, alternatively,
the ion conductor material adopts a mixture of metal salt and colloidal ion conductor material; or the like, or a combination thereof,
the ion conductor material is a mixture of metal salt, quaternary ammonium salt and colloidal ion conductor material.
Of course, the colloidal composite material can be directly made into a film, and the thickness of the film is less than or equal to 50um. When the liquid battery is applied, the thin film is arranged between the corresponding electrode and the ion diaphragm, or the thin film can be compounded on the corresponding electrode and the corresponding ion diaphragm, and the dendrite inhibiting layer I131 and the dendrite inhibiting layer II 132 are formed.
Preferably, the functional metal material in the composite material is metal tin, and the ion conductor material is quaternary ammonium salt.
The structures of the positive electrode 10 and the negative electrode 20 of the present embodiment are the same as those of embodiment 1, and will not be described one by one.
Example 3
Fig. 13 is a schematic structural view of example 3 of the metal electrode-based battery of the present invention. The battery based on the metal electrode of the present embodiment includes a positive electrode 10, a negative electrode 20, and an electrolyte between the positive electrode 10 and the negative electrode 20.
The positive electrode 10 includes a positive electrode active material; the positive active material is prepared by mixing a metal material and a positive material for adjusting potential, or the positive active material is formed by compounding the metal material and at least one layer of the positive material for adjusting potential.
The anode 20 includes an anode active material; the negative electrode active material is made of a metal material, or the negative electrode active material is made of a mixture of a metal material 20a and a negative electrode material 20b for adjusting potential; or the negative active material is formed by compounding a metal material and at least one layer of negative material for adjusting potential.
The electrolyte of the present embodiment employs a solid ion conductor 40. Specifically, a dendrite inhibiting layer III 141 for inhibiting dendrite growth and enabling ionic conduction is arranged between the positive electrode 10 and the solid ion conductor 40, and/or a dendrite inhibiting layer IV 142 for inhibiting dendrite growth and enabling ionic conduction is arranged between the negative electrode 20 and the solid ion conductor 40. In the present embodiment, a dendrite suppression layer iii 141 for suppressing dendrite growth and enabling ionic conduction is provided between the positive electrode 10 and the solid ion conductor 40, and a dendrite suppression layer iv 142 for suppressing dendrite growth and enabling ionic conduction is provided between the negative electrode 20 and the solid ion conductor 40.
Specifically, the dendrite suppression layer iii 141 is composited on the positive electrode 10, or the dendrite suppression layer iii 141 is composited on the solid ion conductor 40; the dendrite suppression layer iv 142 is compounded on the negative electrode 20, or the dendrite suppression layer iv 142 is compounded on the solid ion conductor 40.
As shown in fig. 14, a schematic structural diagram of the case where the dendrite suppression layer iii 141 is combined on the positive electrode 10 and the dendrite suppression layer iv 142 is combined on the negative electrode 20;
as shown in fig. 15, a schematic structural view is shown when the dendrite suppression layer iii 141 is combined with the solid ion conductor 40 and the dendrite suppression layer iv 142 is combined with the solid ion conductor 40.
Needless to say, the dendrite suppression layer iv 142 may be combined with the solid ion conductor 40 when the dendrite suppression layer iii 141 is combined with the positive electrode 10, or the dendrite suppression layer iv 142 may be combined with the negative electrode 20 when the dendrite suppression layer iii 141 is combined with the solid ion conductor 40, which will not be described again.
Furthermore, the dendritic crystal inhibition layer III 141 and the dendritic crystal inhibition layer IV 142 are both made of composite materials for inhibiting dendritic crystal growth, and the composite materials are made of functional metal materials for inhibiting dendritic crystal growth and ion transmission materials for realizing ion conduction in a mixing mode; (ii) a
The functional metal material and the ion conduction material are mixed together by a physical method or a chemical method;
the functional metal material adopts at least one of metal tin, metal titanium, metal tungsten, metal lead and metal aluminum;
the ion conducting material is at least one of metal salt, quaternary ammonium salt and ion conductor material.
The composite material of this example is the same as example 3 and will not be described in detail.
The structures of the positive electrode 10 and the negative electrode 20 of the present embodiment are the same as those of embodiment 1, and will not be described one by one.
Example 4
Fig. 16 is a schematic diagram of a stacked cell based on all-metal electrodes. The present embodiment is based on a stacked cell of all-metal electrodes comprising at least two cells 60 stacked together.
The bipolar current collecting plate 50 which is electrically conductive and ion-isolated is arranged between the anode 10 and the cathode 20 of one battery of two adjacent batteries, and the anode 10 and the cathode 20 of the two adjacent batteries are adjacently arranged; as shown in fig. 16, all the cells are arranged in series.
In two adjacent batteries, the positive electrode 10 of one battery and the positive electrode 10 of the other battery are adjacently arranged, or the negative electrode 20 of one battery and the negative electrode 20 of the other battery are adjacently arranged, and an electronically conductive but ionically isolated bipolar current collecting plate 50 is arranged between the two adjacent positive electrodes 10 or the two adjacent negative electrodes 20, as shown in fig. 17, in this case, all batteries are arranged in parallel.
Specifically, the battery of the present embodiment is the same as that of embodiment 1, embodiment 2 or embodiment 3, and will not be described in detail.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (19)

1. A metal electrode-based battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that:
the positive electrode includes a positive electrode active material;
the positive electrode active material is prepared by mixing a metal material and a positive electrode material for adjusting potential, or the positive electrode active material is prepared by compounding the metal material and at least one layer of positive electrode material for adjusting potential;
the negative electrode includes a negative electrode active material;
the negative active material is made of a metal material; or the like, or, alternatively,
the negative electrode active material is made of a mixture of a metal material and a negative electrode material for adjusting potential; or the like, or a combination thereof,
the negative electrode active material is formed by compounding a metal material and at least one layer of negative electrode material for adjusting potential;
when the lithium ion battery is used for the first time, the battery is charged, and the metal material of the positive electrode is changed into metal ions.
2. The metal electrode-based battery of claim 1, wherein:
the metal material is made of one or at least two of metal magnesium and metal aluminum.
3. The metal electrode-based battery of claim 1, wherein:
the positive electrode material comprises at least one of iron phosphate, lithium cobaltate, manganese phosphate, a ternary positive electrode material, polysulfide and a metal air positive electrode material.
4. The metal electrode-based battery of claim 1, wherein:
the mass ratio of the positive electrode material to the metal material in the positive electrode active material is 5-80%.
5. The metal electrode-based battery according to any one of claims 1 to 4, wherein:
the positive active material is internally provided with a dendrite inhibiting material I for inhibiting dendrite growth, and the dendrite inhibiting material I comprises at least one of metal tin, metal titanium, metal tungsten, metal lead, metal aluminum and quaternary ammonium salt.
6. The metal electrode-based battery of claim 5, wherein:
the mass ratio of the dendrite inhibiting material I to the metal material in the positive electrode active material is 1-100%.
7. The metal electrode-based battery of claim 1, wherein:
the negative electrode material comprises at least one of silicon oxide and derivatives thereof, graphene and derivatives thereof, carbon nanotubes and derivatives thereof, biomass carbon materials and derivatives thereof, lithium-containing polymers and derivatives thereof, and surface functionalized carbon materials.
8. The metal electrode-based battery of claim 1, wherein:
the mass ratio of the negative electrode material to the metal material in the negative electrode active material is 0.01-80%.
9. The metal electrode-based cell of any one of claims 1-4,7 or 8 wherein:
and a dendrite inhibiting material II for inhibiting the growth of dendrites is arranged in the negative active material, and the dendrite inhibiting material II comprises at least one of metal tin, metal titanium, metal tungsten, metal lead, metal aluminum and quaternary ammonium salt.
10. The metal electrode-based battery of claim 9, wherein:
the mass ratio of the dendrite inhibiting material II to the metal material in the negative electrode active material is 1-100%.
11. The metal electrode-based cell of any one of claims 1-4,7 or 8 wherein:
the electrolyte includes an electrolyte solution and a separator disposed between the positive electrode and the negative electrode for ionic conduction.
12. The metal electrode-based battery of claim 11, wherein:
a dendrite inhibiting layer I for inhibiting dendrite growth and conducting ions is arranged between the positive electrode and the diaphragm, and/or,
and a dendrite inhibiting layer II which is used for inhibiting dendrite growth and can conduct ions is arranged between the negative electrode and the diaphragm.
13. The metal electrode-based battery of claim 12, wherein:
the dendrite inhibiting layer I is compounded on the positive electrode, or the dendrite inhibiting layer I is compounded on the diaphragm;
the dendrite inhibiting layer II is compounded on the negative electrode, or the dendrite inhibiting layer II is compounded on the diaphragm.
14. The metal electrode-based battery of claim 12, wherein:
the dendritic crystal inhibition layer I and the dendritic crystal inhibition layer II are both made of composite materials for inhibiting dendritic crystal growth, and the composite materials are made of functional metal materials for inhibiting dendritic crystal growth and ion transmission materials for realizing ion conduction in a mixed mode;
the functional metal material is at least one of metal tin, metal titanium, metal tungsten, metal lead and metal aluminum;
the ion conducting material adopts at least one of metal salt, quaternary ammonium salt and ion conductor material.
15. The metal electrode-based cell of any one of claims 1-4,7 or 8 wherein:
the electrolyte adopts a solid ion conductor.
16. The metal electrode-based battery of claim 15, wherein:
a dendrite inhibiting layer III for inhibiting growth of dendrite and enabling ionic conduction is arranged between the positive electrode and the solid ion conductor, and/or,
and a dendrite inhibiting layer IV which is used for inhibiting dendrite growth and can be conducted by ions is arranged between the negative electrode and the solid ion conductor.
17. The metal electrode-based battery of claim 16, wherein:
the dendrite inhibiting layer III is compounded on the positive electrode, or the dendrite inhibiting layer III is compounded on the solid ion conductor;
and the dendritic crystal inhibition layer IV is compounded on the negative electrode, or the dendritic crystal inhibition layer IV is compounded on the solid ion conductor.
18. The metal electrode-based battery of claim 16, wherein:
the dendritic crystal inhibition layer III and the dendritic crystal inhibition layer IV are both made of composite materials for inhibiting dendritic crystal growth, and the composite materials are made of functional metal materials for inhibiting dendritic crystal growth and ion transmission materials for realizing ion conduction in a mixed mode;
the functional metal material is at least one of metal tin, metal titanium, metal tungsten, metal lead and metal aluminum;
the ion conducting material adopts at least one of metal salt, quaternary ammonium salt and ion conductor material.
19. A metal electrode based laminate battery, characterized in that:
comprising at least two cells of any one of claims 1-18 laminated together;
in two adjacent batteries, the positive electrode of one battery and the negative electrode of the other battery are adjacently arranged, and a bipolar current collecting plate which is electrically conductive and ion-isolated is arranged between the adjacent positive electrode and the adjacent negative electrode; or the like, or, alternatively,
and in two adjacent batteries, the positive electrode of one battery and the positive electrode of the other battery are adjacently arranged, or the negative electrode of one battery and the negative electrode of the other battery are adjacently arranged, and an electronically conductive and ion-isolated bipolar current collecting plate is arranged between the two adjacent positive electrodes or the two adjacent negative electrodes.
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JPH0689742A (en) * 1992-09-09 1994-03-29 Hitachi Ltd Nonaqueous secondary battery
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CN103038918A (en) * 2010-07-30 2013-04-10 日产自动车株式会社 Laminated cell
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