CN110752346B - Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery - Google Patents

Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery Download PDF

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CN110752346B
CN110752346B CN201810811529.XA CN201810811529A CN110752346B CN 110752346 B CN110752346 B CN 110752346B CN 201810811529 A CN201810811529 A CN 201810811529A CN 110752346 B CN110752346 B CN 110752346B
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metal
layer
porous
negative electrode
deposition
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CN110752346A (en
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陈永翀
刘丹丹
滕勇强
何颖源
王馨
张彬
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Nanjing Jingyu Energy Co.,Ltd.
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Beijing Hawaga Power Storage 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a back deposition type metal cathode, which comprises a nonporous electronic insulation layer and two metal cathode parts, wherein each metal cathode part comprises a cathode current collecting layer and a porous electronic insulation layer compounded on one side of the cathode current collecting layer, the cathode current collecting layers of the two metal cathode parts are oppositely arranged, the nonporous electronic insulation layer is arranged between the two metal cathode parts and used for preventing ions from penetrating through and is electrically insulated, ion penetrating through holes are arranged at corresponding positions on the porous electronic insulation layer and the cathode current collecting layer, and the area of the ion penetrating through holes of the porous electronic insulation layer is smaller than or equal to the area of the ion penetrating through holes of the cathode current collecting layer. The back deposition type metal cathode fundamentally inhibits the growth of dendrite, greatly improves the safety of the secondary battery, and effectively improves the electrochemical performance of the secondary battery. The invention further provides a back-deposited metal negative electrode battery.

Description

Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery
Technical Field
The invention belongs to the technical field of electrochemical secondary batteries, and particularly relates to a back-deposition type metal cathode and a back-deposition type metal cathode battery.
Background
With the rapid development of portable electronic devices and electric vehicles, the demand for secondary batteries having high energy density is more urgent. Among them, for the electrode material, the metal negative electrode is gradually a strong candidate for a novel high-efficiency negative electrode material system due to the advantages of high theoretical specific capacity, wide raw materials, low raw material price and the like. For example, metallic lithium electrodes, have extremely high theoretical specific capacity (3860mAh/g), most negative reduction potential, and extremely low density; the metal zinc electrode has the advantages of low equilibrium potential, rich raw materials, environmental friendliness, good electrochemical reversibility and the like. In recent years, magnesium, sodium, potassium, calcium, and the like have been widely studied as metal negative electrode materials.
However, in the multiple cycles of the secondary battery, metal ions are directly deposited on the surface of the metal cathode opposite to the anode active material through electrochemical reaction (namely, forward deposition), and the problems of dendritic crystal growth, pulverization and shedding (such as 'dead lithium'), passivation and the like are easy to occur, so that the coulombic efficiency is low, the cycle performance is poor, and even internal short circuit occurs, so that safety accidents such as thermal failure or explosion and the like are caused. In order to inhibit the dendritic crystal growth of a metal cathode in the process of charging and discharging of a battery, an effective protective film is formed on the surface of the metal cathode opposite to an anode active material by a physical or chemical method so as to isolate the direct contact between the metal cathode and an electrolyte; or surface modification is carried out on the isolating layer, a protective layer is added between the isolating layer and the metal negative electrode, and the like. However, from the surface modification effect of the metal negative electrode or the isolation layer, the methods only improve the dendrite to a certain extent, cannot fundamentally inhibit the generation of the dendrite, and are not suitable for large-area preparation or commercial application because the preparation process conditions of the protective film are harsh and the preparation cost is high.
Therefore, the search for a metal negative electrode protection technology that effectively suppresses dendrite growth becomes a key and hot spot for the development of high energy density secondary batteries.
Disclosure of Invention
Aiming at the problems, the invention provides a novel back-deposition type metal cathode, the structure of the metal cathode utilizes the dynamic principle, and through changing the migration path and the deposition site of metal ions, the metal ions are uniformly deposited into a metal layer on the back of the metal cathode through electrochemical reduction reaction, so that the growth of dendrites on the front of the metal cathode is fundamentally inhibited, and the problem of short circuit of a battery caused by the penetration of the dendrites on an isolation layer is avoided. The back deposition type metal cathode can fully utilize the dynamic principle that the diffusion migration distance required when metal ions reach the front end of the dendrite on the back of the metal cathode to be deposited is larger than the diffusion migration distance when the metal ions are directly deposited on the back of the metal cathode, so that the metal ions are more prone to being directly deposited on the back of the metal cathode to improve the uniformity of metal deposition on the back. In addition, the back deposition type metal cathode not only greatly improves the safety performance of the battery, but also ensures excellent electrochemical performance.
The technical scheme provided by the invention is as follows:
the invention provides a back deposition type metal cathode, which is characterized by comprising a nonporous electronic insulating layer and two metal cathode parts, wherein each metal cathode part comprises a cathode current collecting layer and a porous electronic insulating layer compounded on one side of the cathode current collecting layer, the cathode current collecting layers of the two metal cathode parts are oppositely arranged, the nonporous electronic insulating layer is arranged between the two metal cathode parts and used for preventing ions from penetrating and electrically insulating, a deposition cavity is formed between the metal cathode parts and the nonporous electronic insulating layer, ion penetrating through holes for ions to penetrate are arranged at corresponding positions on the porous electronic insulating layer and the cathode current collecting layer, the ions penetrate through the ion penetrating through holes and are deposited as a metal layer on the surface of the non-contact side of the cathode current collecting layer and the porous electronic insulating layer through electrochemical reduction reaction, and the area of the ion penetrating through holes of the porous electronic insulating layer is less than or equal to the area of the ion penetrating through holes of the cathode current collecting layer.
The back deposition type metal cathode structure designed by the invention fundamentally solves the problem of dendritic crystal growth easily occurring on the surface of the traditional metal cathode. Specifically, in the process of multiple cycles and overcharge and overdischarge of the secondary battery, dendrites are easily formed on the front surface of the conventional metal negative electrode (i.e., the surface of the metal negative electrode opposite to the positive electrode active material), and along with the increase of the number of cycles, the dendrites rapidly grow and pierce through the isolation layer to contact with the positive electrode, so that the internal short circuit of the battery is caused, and safety accidents such as thermal failure or explosion are caused. In the back deposition type metal negative electrode, the porous electronic insulating layer capable of shielding ions and electrons from passing through is compounded on one side of the negative electrode current collecting layer of the metal negative electrode part, so that the metal ions can not obtain electrons on the front surface of the metal negative electrode part (namely the surface of the metal negative electrode part opposite to the positive electrode active material) in the process of multiple cycles of the secondary battery, and the dendritic crystals are prevented from being separated out on the front surface of the metal negative electrode part. On the other hand, the ion penetration through hole is arranged at the corresponding position of the negative current collecting layer of the metal negative part and the porous electronic insulating layer to control the migration path of metal ions, so that the metal ions penetrate through the ion penetration through hole and are deposited into a metal layer through electrochemical reaction on the back surface of the metal negative part, namely the surface of the non-contact side of the negative current collecting layer and the porous electronic insulating layer; meanwhile, the diffusion migration distance required when the metal ions reach the front end of the dendrite on the back of the metal negative part for deposition is larger than the diffusion migration distance required when the metal ions directly reach the back of the metal negative part for deposition, so that the metal ions are more prone to being directly deposited on the back of the metal negative part by utilizing the dynamic principle, the growth of the dendrite on the back of the metal negative part is completely inhibited, and the back deposition of the metal ions is more uniform. It is to be emphasized here that the area of the ion-penetrating through-holes of the porous electron insulating layer should be equal to or less than the area of the ion-penetrating through-holes of the negative current collecting layer. If the ion penetration area of the porous electron insulation layer is larger than the ion penetration area of the negative current collector layer, the metal ions can directly migrate to the non-recombination area on the contact side of the negative current collector layer and the porous electron insulation layer, so that dendrites preferentially grow in the non-recombination area, and the back deposition path of the metal ions is blocked.
In the back deposition type metal negative electrode of the present invention, the negative current collecting layers of the two metal negative electrode portions are placed opposite to each other, and a non-porous electronic insulating layer for preventing ions from passing therethrough and for electronic insulation is provided between the two metal negative electrode portions, thereby avoiding a situation where metal ions may be preferentially deposited on the other metal negative electrode portion. This is because, without providing a non-porous electron insulating layer, the diffusion migration distance required for the metal ions to reach the back surface of the metal negative electrode portion after passing through the ion-penetrating through holes is significantly longer than the diffusion migration distance required to reach the surface of the negative current collecting layer of the other metal negative electrode portion based on the kinetic principle, which is contrary to the design of the back deposition. On the other hand, if a non-porous electronic insulating layer is not provided, when a metal layer deposited on the back surface of the metal negative electrode part is accumulated to a certain thickness during the overcharge of the secondary battery, ions from the other metal negative electrode part may penetrate through the through-holes, thereby penetrating the separator to cause an internal short circuit of the battery.
According to the invention, a deposition cavity is formed between the metal cathode part and the nonporous electronic insulation layer, the deposition cavity is a deposition space capable of accommodating the deposition of the metal cathode, and the thickness of the deposition cavity can be 0.1-2 mm, and is preferably 0.5-1.5 mm.
Preferably, an insulating support member may be provided in the deposition chamber to maintain a deposition space between the metallic negative electrode portion and the non-porous electronic insulating layer. The insulating support component can comprise one or more of a gasket, a strip-shaped wavy member, a porous insulating material layer, a porous sheet with a protruding part on the surface and the like.
Preferably, the porous insulating material layer can be a porous electronic insulating material which is resistant to electrolyte corrosion and is penetrated by ions, and comprises a porous insulating composite material such as a porous insulating polymer material, a porous insulating inorganic non-metallic material, a composite of an insulating inorganic non-metallic material and an organic polymer material, and the porosity of any one of the porous materials can be 30-90%; the porous insulating polymer material can be one or more selected from natural cotton and linen, terylene, aramid fiber, nylon, polyolefin, polytetrafluoroethylene, polyvinylidene fluoride and the like, the insulating inorganic non-metallic material can be one or more selected from glass fiber cloth, ceramic fiber paper porous insulating inorganic non-metallic material and the like or one or more selected from silicon oxide, silicon nitride, aluminum oxide, aluminum nitride and the like, and the organic polymer material in the porous insulating composite material can be one or more selected from terylene, aramid fiber, nylon, polyolefin, polytetrafluoroethylene, polyvinylidene fluoride and the like.
The present inventors have also surprisingly found that the use of a porous electronically insulating material as the insulating support member, in addition to acting to support the deposition chamber, results in a more uniform deposition of metal ions on the back of the metallic negative electrode portion. This is probably due to the fact that the three-dimensional pore structure of the porous electron insulating layer itself promotes redistribution of the metal ions during deposition, thereby avoiding the adverse effects of locally depositing too thick a metal layer.
According to the present invention, the equivalent aperture of the ion penetration through hole of the negative current collecting layer of the metal negative part may be 0.2mm to 5mm, preferably 0.4mm to 2.5mm, and more preferably 0.6mm to 1.8 mm; the center distance of the holes can be 0.5 mm-8 mm; the porosity may be 5% to 70%, preferably 30% to 60%, more preferably 40% to 50%.
According to the present invention, the equivalent aperture of the ion penetration through hole of the porous electron insulating layer of the metal negative electrode part may be 0.1mm to 5mm, preferably 0.2mm to 2.5mm, more preferably 0.4mm to 1.8 mm; the center distance of the holes can be 0.5 mm-8 mm; the porosity may be 5% to 70%, preferably 30% to 60%, more preferably 40% to 50%.
The reason why the ion-permeable through hole of the present invention satisfies the above conditions is as follows: if the equivalent aperture of the ion penetration through hole is too large, the longer the distance from the metal ion from the positive electrode, which is opposite to the center direction of the ion penetration through hole, to the deposition site on the back of the metal negative electrode part is, the polarization of the battery is increased, and the cycle performance is degraded; if the equivalent pore diameter of the ion penetration through-hole is too small, the migration rate of metal ions is reduced, and even the ion penetration through-hole is clogged. Further, if the porosity of the ion penetration through-hole is too large, the unit deposition amount of metal ions on the back surface of the metal negative electrode part is too small, resulting in a decrease in battery capacity; if the porosity of the ion penetrating through the through-hole is too small, the migration path of the metal ions is blocked, resulting in a decrease in the overall performance of the battery.
According to the present invention, the shape of the ion penetration through hole may include one or more of a circle, an elliptical hole, a polygon, and the like.
Preferably, the porous electronic insulating layer of the metal negative electrode part can be compounded on the side wall of the ion penetrating through hole of the negative electrode current collecting layer. When the equivalent aperture of the ion penetration through hole of the negative current collecting layer is equal to the equivalent aperture of the ion penetration through hole of the porous electronic insulating layer, metal ions are preferentially deposited on the side wall of the ion penetration through hole of the negative current collecting layer, so that dendrites grow sharply towards the center of the through hole along the side wall of the through hole, and finally the ion penetration through hole is blocked, and the back deposition path of the metal ions is blocked. Therefore, in the case where the side wall of the ion penetration through hole of the negative current collecting layer is also compounded with the porous electron insulating layer, the dendritic growth at the side wall can be further suppressed.
According to the invention, the porous electronic insulating layer of the metal negative electrode part can be tightly compounded on one side of the negative electrode current collecting layer and the side wall of the ion penetration through hole thereof in one or more modes of bonding, coating, mechanical pressing and the like. Wherein, the bonding mode can comprise hot melt adhesive bonding, adhesive bonding and the like; the adhesive can be one or more selected from thermosetting polymer materials, thermoplastic polymer materials and the like, wherein the thermosetting polymer materials can be one or more selected from epoxy resins, polyurethanes, silicones, polyimides and the like, and the thermoplastic polymer materials can be one or more selected from poly (methyl) acrylates, polyolefins, methanol thermoplastic materials, phenolic-epoxy modified materials and the like.
According to the present invention, the porous electron insulating layer of the metal negative electrode part may be an inorganic material or an organic material capable of shielding ions and electrons from passing therethrough; wherein, the inorganic material can be one or more selected from silicon oxide, silicon nitride, aluminum oxide, aluminum nitride and the like, and the organic material can be one or more selected from polyimide, polyolefin, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyamide, styrene butadiene rubber and the like; the thickness of the porous electron insulating layer may be 5 μm to 500 μm, preferably 10 μm to 200 μm, and more preferably 15 μm to 50 μm.
According to the present invention, the negative current collecting layer of the metal negative electrode part may be an electron conductive layer having a thickness of 0.01 to 2000 μm, preferably 0.05 to 1000 μm, and more preferably 0.5 to 800 μm;
the electronic conducting layer can be one or more of foil-shaped, plate-shaped, net-shaped, sheet-shaped, porous foam-shaped and other conducting metal layers; the conductive metal layer can be made of one or more materials selected from lithium, zinc, magnesium, sodium, potassium, calcium, aluminum, iron, stainless steel, nickel, titanium, tin, copper, tin-plated copper, nickel-plated copper and the like; preferably, the surface of the conductive metal layer is free of oxidation, and is smooth on two sides and has single-side burrs or/and double-side burrs;
or the electronic conducting layer can be one or more of carbon fiber conducting cloth, metal wire and organic fiber mixed conducting cloth and the like; the metal wire can be made of one or more of lithium, zinc, magnesium, sodium, potassium, calcium, aluminum, iron, stainless steel, nickel, titanium, tin, copper, tin-plated copper, nickel-plated copper and the like, and the organic fiber wire can be one or more of natural cotton and linen, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene, polytetrafluoroethylene and the like.
Or the electronic conducting layer can be one or more of a conducting metal layer, a conducting cloth, an inorganic non-metallic material, a porous organic material and the like, the surface of which is compounded with a negative conducting particle layer or a metal film; the negative conductive particle layer can be a conductive agent or a mixture or a compound of the conductive agent and a negative active material, the conductive agent can be one or more selected from carbon black, graphene, carbon nanotubes, carbon fibers, amorphous carbon, metal conductive particles, metal conductive fibers and the like, and the metal conductive particles or the metal conductive fibers can be one or more selected from aluminum, stainless steel, silver and the like; the metal film can be one or more selected from lithium, zinc, magnesium, sodium, potassium, calcium, aluminum, iron, stainless steel, nickel, titanium, tin, copper, tin-plated copper, nickel-plated copper and the like; the inorganic non-metallic material can be one or more selected from glass fiber non-woven fabrics, ceramic fiber paper and the like; the porous organic material can be one or more selected from natural cotton hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene, polytetrafluoroethylene and the like.
According to the invention, the non-porous electronic insulating layer is resistant to electrolyte corrosion and electrochemically stable, and can be an inorganic material or an organic material capable of shielding ions and electrons from passing through; wherein, the inorganic material is selected from one or more of silicon oxide, silicon nitride, aluminum oxide, aluminum nitride and the like, and the organic material is selected from one or more of polyimide, polyolefin, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyamide, styrene butadiene rubber and the like; the thickness of the non-porous electron insulating layer is 5 μm to 1000 μm, preferably 10 μm to 300 μm, and more preferably 20 μm to 100 μm.
Preferably, the non-porous electronic insulating layer may comprise one or more of a non-porous film, a plate, a sheet, and the like.
Preferably, the non-porous electronic insulating layer may have blind holes or a rough surface.
According to the invention, the deposited metal ions may comprise Li+、Zn2+、Mg2+、Na+、K+、Ca2+、Al3+、Fe2+Etc., preferably Li+、Na+Or Zn2+。
The invention also provides a back deposition type metal negative electrode battery, wherein the back deposition type metal negative electrode battery can comprise a battery core, electrolyte, a battery shell, a positive electrode terminal and a negative electrode terminal; the battery core can comprise a positive plate, an isolation layer and the back deposition type metal negative pole, wherein the positive plates and the back deposition type metal negative poles are alternately stacked, and the isolation layer is arranged between the positive plates and the back deposition type metal negative poles.
The positive plate can be provided with part or all of the positive active conductive particles which are fixed in a non-bonding mode, the positive active conductive particles can be a conductive agent, or a compound or a mixture of a positive active material and the conductive agent, and the compounding or mixing mode of the positive active material and the conductive agent can comprise coating, bonding or mechanical mixing. The positive active conductive particles may be in a semi-dry state containing a part of liquid, such as a paste, slurry, gel or gel; preferably, the positive active conductive particles may be in a dry bulk state, such as powder, pressed sheet, pressed block, etc., and the porosity of the bulk state may be greater than 5% and less than 60%. The positive active conductive particles in a dry accumulation state are adopted, and the positive slurry is formed by fully soaking the electrolyte after the electrolyte is injected. The mass ratio of the positive electrode active conductive particles to the positive electrode slurry may be 10% to 90%, preferably 15% to 80%. The average particle diameter of the positive electrode active conductive particles can be 0.05-500 mu m, and the mass ratio of the positive electrode active material to the conductive agent can be 20-98: 80-2.
Or the positive plate can comprise a positive current collecting layer and a positive material layer fixed on one side or two sides of the positive current collecting layer, wherein the positive material layer can be a mixture of a positive active material, a conductive agent and/or an adhesive, and the mass percentage of the positive material is 40-95%, 1-30% and 0-20% respectively. The mixture is fixed on one side or two sides of the anode current collecting layer by one or more modes of a casting method, a dipping method or a flow coating method, spraying, brushing or bonding, mechanical rolling and the like.
Preferably, the positive electrode sheet material includes, but is not limited to, the following mentioned materials:
when the back-deposition type metal negative electrode battery of the present invention is a lithium secondary battery, the material of the positive electrode sheet may be one or more selected from lithium iron phosphate, lithium manganese phosphate, lithium silicate, lithium iron silicate, sulfate compounds, sulfur-carbon compounds, elemental sulfur, titanium sulfur compounds, molybdenum sulfur compounds, iron sulfur compounds, doped lithium manganese oxides, lithium cobalt oxides, lithium titanium oxides, lithium vanadium oxides, lithium nickel manganese oxides, lithium nickel cobalt aluminum oxides, lithium nickel cobalt manganese oxides, lithium iron nickel manganese oxides, and the like.
When the back-deposited metal negative electrode battery of the present invention is a zinc secondary battery, the material of the positive electrode sheet may be selected from manganese dioxide, vanadium pentoxide, metal ferricyanide, and ferric (vi) acid salt (e.g., BaFe)2O4、K2FeO4) And the like.
When the back deposition type metal anode battery of the present invention is a magnesium secondary battery, the material of the positive electrode sheet may be selected from transition metal sulfides (e.g., MS)2、NbS3Chevrel phase sulfides), transition metal oxides (e.g. V)2O5、MV3O8Hydrate, V6O13、MoO3) Oxide having spinel structure (e.g. Co)3O4、Mn3O4、Pb3O4、Mn2.15Co0.37O4Todorokite type MgxMnO2·yH2O、α-U3O8、RuO2、WO3、Mn2O3、PbO2) Polyanionic compounds (e.g. Mg)0.5Ti2(PO4)3、Mg0.5+y(FeyTi1-y)2(PO4)3、MgxMySiO4(M＝Fe、Ni、Mn，x+y＝2))、MgxMo3S4、V2O5Aerogel, V2O5gel/C composite, graphene-like structured MoS2、MoB2Or TiB2、ZrB2、MgV2O6、MgTi2O5And the like.
When the back-deposition type metal negative electrode battery of the present invention is a sodium secondary battery, the material of the positive electrode sheet may be selected from sulfur, air, transition metal oxides (e.g., Na)xMeO2Wherein Me represents transition metal selected from one or more of Mn, Fe, Ni, Co, V, Cu, Cr, etc.), polyanion material (such as A)xMy[(XOm)n-]zWherein A represents Li or Na, M represents a metal ion of variable valency, X represents P, S, V or Si), mixed anionic compounds (e.g. XO4F (X ═ P or S), PO4P2O7) Prussian blue compounds (e.g. A)xMA[MB(CN)6]·zH2O (A represents an alkali metal ion, M)AAnd MBEach represents a transition metal ion, such as Ni2+、Cu2+、Fe2+、Mn2+、Co2+With face centered cubic structure), small organic molecules or polymers containing quinones, anhydrides, amides or phenols, amorphous materials (e.g. FePO)4、V2O5、NaFePO4FeOOF) and the like.
More preferably, the positive electrode sheet material for the sodium secondary battery may be selected from NaxCoO2、NaCrO2、NaNiO2，NaxMnO2、NaxTiyMnzO2、NaFePO4、Na3V2(PO4)3、Na2FeP2O7、Na2MnP2O7、NaxFey(SO4)z、Nax(Fe1- yMny)z(SO4)3、Na2+2xMn2-x(SO4)3、Na2Mg(SO4)2·4H2O、NaxFeFe(CN)6、AxMnFe(CN)6、AxCoFe(CN)6、AxNiFe(CN)6、AxCuFe(CN)6And the like.
When the back-deposition type metal anode battery of the present invention is a potassium secondary battery, the material of the positive electrode sheet may be selected from prussian blue and the like (e.g., a)xMa[Mb(CN)6]·zH2O, wherein A represents an alkali metal element, Ma and Mb each represent a transition metal element having a face-centered cubic structure), a transition metal oxide (e.g., A)xMO2(a ═ Li, Na, or K, M ═ Co, Ni, or Mn)), and polyanionic materials (e.g., a ═ Li, Na, or K), and the likexMy[(XOm)n-]Wherein A represents Li, Na or K, M represents transition metal ions, and X represents P, V, S or Si) or the like.
When the back-deposition type metal negative electrode battery of the invention is a calcium secondary battery, the material of the positive electrode sheet can be selected from graphite and CaCo2O4Prussian blue and analogues thereof (e.g. K)xMFe(CN)6·nH2O), potassium barium hexacyanoferrate (K)2BaFe(CN)6) And the like.
When the back deposition type metal negative electrode battery of the present invention is an aluminum secondary battery, the material of the positive electrode sheet may be selected from the group consisting of conductive polymers (e.g., sulfur-carbon composite, polyacrylonitrile sulfide, polysulfone, polyacetylene sulfide), transition metal oxides (e.g., MnO), and the like2、V2O5Complex metal oxides such as (Al)xM1-x)2(M'O4)3) Wherein M represents M2 aM3 bM4 c，M2Represents at least one divalent metal element selected from Mg, Ca, Sr, Ba, etc., M3Represents at least one trivalent metal element selected from Sc, Y, Ga, In, etc., M4Represents at least one tetravalent metal element selected from Zr, Hf, etc., and M' represents a hexavalent metal element selected from W or M), metal chloride, Cl2Sulfur and compounds of elements of the same group (e.g. FeS)2、FeS、TiS2、Cr2S3、NaFeS2、CoS3、NiS、Ni3S2、MoS3) And the like.
When the back-deposition type metal negative electrode battery of the present invention is an iron secondary battery, the material of the positive electrode sheet may be selected from nickel, high iron (vi) acid salts (e.g., BaFe)2O4、K2FeO4) And the like.
The invention has the advantages that:
(1) the back deposition type metal cathode structure changes the migration path and deposition sites of metal ions by using the principle of dynamics, and realizes the uniform deposition of the metal ions on the back of the metal cathode part, thereby fundamentally inhibiting the growth of dendrites and greatly improving the safety of secondary batteries.
(2) Through the reasonable setting of the aperture and the porosity of the ion penetrating through hole in the back deposition type metal negative electrode, the distance from the metal ions to the deposition site on the back of the metal negative electrode part is reduced, the migration rate is improved, the unit deposition amount of the metal ions on the back of the metal negative electrode part is increased, and the electrochemical performance of the secondary battery is effectively improved.
(3) The metal cathode protection technology is convenient to operate and control, can effectively reduce the raw material cost and the production energy consumption, and does not produce environmental pollution, so the metal cathode protection technology is particularly suitable for large-scale industrial production.
Drawings
Fig. 1 is a schematic structural view of a back-deposited metal anode according to the present invention.
Fig. 2 is a schematic diagram of lithium ion deposition during charging of a lithium negative electrode battery, and fig. 2 (a) is a schematic diagram of lithium ion deposition during charging of a conventional lithium negative electrode battery; fig. 2 (b) is a schematic diagram of lithium ion deposition during charging of a back-deposition type lithium negative electrode battery according to the present invention.
Fig. 3 is a schematic structural diagram of a back-deposited metal anode according to an embodiment of the present invention.
Fig. 4 is a schematic structural view of a back-deposited metal anode according to another embodiment of the present invention, in which an insulating support member is disposed in a deposition chamber. Fig. 4 (a) is a schematic structural view of a porous sheet having a convex portion on a surface thereof as an insulating support member, fig. 4 (b) is a schematic sectional view of a porous insulating material layer which can be used as an insulating support member, fig. 4 (c) is a schematic sectional view of a strip-shaped wavy member which can be used as an insulating support member, and fig. 4 (d) is a schematic sectional view of a gasket which can be used as an insulating support member.
Fig. 5 is a test chart of electrochemical performance of a back-deposition type lithium negative electrode battery according to an embodiment of the present invention, wherein (a) of fig. 5 is a charge and discharge test chart; fig. 5 (b) is a cycle performance test chart.
Fig. 6 is a test chart of electrochemical properties of a back-deposition type lithium anode battery of a comparative example, in which (a) of fig. 6 is a charge and discharge test chart; fig. 6 (b) is a cycle performance test chart.
List of reference numerals
1-Positive plate
2-isolation layer
3-lithium negative electrode of existing lithium negative electrode batteries
4-Back-deposited lithium negative electrode according to the invention
401-negative current collector layer
402, 402' -perforated electronic insulating layer
403-non-porous electronic insulation layer
404-ion penetration through hole
a-region of ion-penetrating through-hole of porous electron-insulating layer
b-region of the negative current collector where ions penetrate the through-hole
405-deposition Chamber
406 porous sheet with protrusions on the surface
407 porous insulating Material layer
408-strip-shaped wavy component
409-washer
Detailed Description
The invention will be further explained by embodiments in conjunction with the drawings.
Fig. 1 is a schematic structural view of a back-deposited metal anode according to the present invention. The back-deposited metal negative electrode 4 comprises a non-porous electronic insulating layer 403 and two metal negative electrode parts, each metal negative electrode part comprises a negative current collecting layer 401 and a porous electronic insulating layer 402 compounded on one side of the negative current collecting layer 401, the negative current collecting layers 401 of the two metal negative electrode parts are oppositely arranged, the non-porous electronic insulating layer 403 is arranged between the two metal negative electrode parts for preventing ions from passing through and electrically insulating, and a deposition cavity 405 is formed between the metal negative electrode parts and the non-porous electronic insulating layer 401, wherein ion penetrating through holes 404 for ions to pass through are arranged at corresponding positions on the porous electronic insulating layer 402 and the negative current collecting layer 401, and the area a of the ion penetrating through holes 404 of the porous electronic insulating layer 402 is smaller than or equal to the area b of the ion penetrating through holes 404 of the negative current collecting layer 401.
The porous electronic insulating layer 402 and the ion penetration through hole 404 work together to control the migration path and deposition site of metal ions, so that the metal ions penetrate through the ion penetration through hole 404 and are deposited as a metal layer on the surface of the non-contact side of the negative current collecting layer 401 and the porous electronic insulating layer 402 through electrochemical reduction reaction, and thus the metal ions are uniformly deposited on the back surface of the metal negative part. Meanwhile, the non-porous electronic insulating layer 403 can not only control the back deposition path of metal ions, but also avoid the occurrence of internal short circuit caused by over-charging of the battery.
Fig. 2 is a schematic diagram of lithium ion deposition during charging of a lithium negative electrode battery. Wherein, fig. 2 (a) is a schematic diagram of lithium ion deposition during charging of a conventional lithium negative electrode battery; fig. 2 (b) is a schematic diagram of lithium ion deposition during charging of a back-deposition type lithium negative electrode battery according to the present invention. As can be seen from the migration path of lithium ions in fig. 2 (b), lithium ions do not get electrons at the front surface of the metal negative electrode part, but directly deposit as a metal layer at the back surface of the metal negative electrode part after passing through the ion penetration through hole, i.e., at the surface of the negative current collecting layer 401 on the side not in contact with the porous electron insulating layer 402, thereby suppressing dendrite generation.
Fig. 3 is a schematic structural diagram of a back-deposited metal anode according to an embodiment of the present invention. In this embodiment, the porous electron insulating layer 402' of the metal negative electrode portion is compounded on the side of the negative current collecting layer 401, and also compounded on the side wall of the ion-permeable through hole of the negative current collecting layer 401. This prevents the metal ions from being preferentially deposited on the side walls of the ion-permeable through holes of the negative current collecting layer 401 when the equivalent aperture of the ion-permeable through holes of the negative current collecting layer 401 is equivalent to the equivalent aperture of the ion-permeable through holes of the porous electron insulating layer 402', thereby further suppressing the growth of dendrites on the side walls and improving the uniformity of the deposition of the metal ions on the back surface of the metal negative electrode part.
Fig. 4 is a schematic structural view of a back-deposited metal anode according to another embodiment of the present invention, in which an insulating support member is disposed in a deposition chamber. Fig. 4 (a) is a schematic structural view of a porous sheet 406 provided with projections on the surface thereof as an insulating support member, fig. 4 (b) is a schematic sectional view of a porous insulating material layer 407 that can serve as an insulating support member, fig. 4 (c) is a schematic sectional view of a strip-like wavy member 408 that can serve as an insulating support member, and fig. 4 (d) is a schematic sectional view of a gasket 409 that can serve as an insulating support member.
In addition to the insulating support member serving to maintain the deposition space between the metallic negative electrode portion and the non-porous electronic insulating layer such that the thickness of the deposition space is 0.1mm to 2mm, the three-dimensional pore structure of the porous insulating material layer 407 in particular also allows for more uniform deposition of metal ions on the back side of the metallic negative electrode portion.
Examples
Preparation of metal negative electrode part of back-deposited lithium negative electrode:
in a first step, a copper mesh (mesh is diamond-shaped, equivalent diameter is about 1mm, porosity is 45%) having a diameter of 19mm and a thickness of 40 μm is pretreated at room temperature to remove surface impurities.
And secondly, soaking the PET non-woven fabric with the same size in an NMP solution with the PVDF content of 5% for 10 minutes, covering the upper surface of the copper mesh (the lower surface of the copper mesh is tightly attached to a layer of aluminum foil), standing at normal temperature for 3 hours, then moving to a 60 ℃ oven, and continuously drying for 24 hours. And then removing the aluminum foil to obtain a copper mesh with one side compounded with PVDF and PET non-woven fabrics as a metal negative electrode part.
Preparing a back deposition type lithium cathode half cell:
taking a lithium iron phosphate pressed powder pole piece with the diameter of 17mm as a positive pole piece, taking a polypropylene film of Celgard corporation in America as an isolation layer, and taking 1M LiPF6And (EC + DMC) (1:1w/w) is used as an electrolyte and assembled into a button cell together with the metal negative part. In order to give a space for back deposition of lithium ions, a copper ring gasket (17 mm in inside diameter) of 1mm thickness was provided on the back of the copper mesh, while the side of the copper ring gasket facing the back of the copper mesh was covered with a polypropylene film (20 μm in thickness).
Comparative examples
Preparation of a metal negative electrode part of a back deposition type lithium negative electrode:
first, a copper foil having a diameter of 30mm and a thickness of 16 μm was pretreated at room temperature to remove surface impurities. And then, moving the pretreated copper foil between an upper die and a lower die of an airflow punching device, and punching a circular hole with the diameter of 12mm at the middle position of the copper foil by utilizing high-pressure hot airflow with the temperature of 100 ℃ and the pressure of 4 MPa.
And secondly, covering one side of the copper foil with the circular hole at the center with a polypropylene film with the diameter of 32mm and the thickness of 20 microns by using an epoxy resin adhesive, and covering the other side of the copper foil with a polypropylene film with the diameter of 16mm and the thickness of 20 microns. Then, a circular hole with the diameter of 8mm is punched at the middle position of the copper foil with the polypropylene films compounded on the two sides, and a metal negative electrode part is obtained.
Preparing a back deposition type lithium cathode half cell:
the lithium iron phosphate pressed powder pole piece with the diameter of 8mm is used as a positive pole piece, a polypropylene film of American Celgard company is used as an isolation layer, and 1M LiPF6And (EC + DMC) (1:1w/w) is used as an electrolyte and assembled into a button cell together with the metal negative part. To give a back deposition space for lithium ions, a 1mm thick gasket (internal diameter 7mm) was placed on the side of the copper mesh compounded with a 16mm diameter polypropylene film.
Electrochemical performance test
Electrochemical performance tests were performed on the back deposition lithium negative electrode battery of the embodiment of the present invention and the back deposition lithium negative electrode battery of the comparative example, respectively, wherein charging and discharging were performed in a constant current mode, a current was set to 2mA, and a voltage range was set to 2.0V to 4.0V. The test results are shown in fig. 5 and 6.
In the back-deposition type lithium negative electrode half cell of the embodiment of the invention, when the equivalent pore diameter and the porosity of the ion penetration through hole are in a specific range, the distance distribution of deposition sites from the positive electrode to the back surface of the metal negative electrode is uniform, so that the back deposition uniformity of lithium ions is improved. As can be seen from a comparison of fig. 5 (a) and fig. 6 (a), the back-deposited lithium anode half-cell according to the example of the present invention has less capacity fade and polarization after the first charge and discharge. In the comparative example, however, since the equivalent aperture of the ion penetration through hole is excessively large, the difference in the distance of the lithium ions reaching the deposition site on the back surface of the metal negative electrode part is increased, resulting in severe capacity fade and polarization of the half cell.
As can be seen from a comparison of fig. 5 (b) and fig. 6 (b), the capacity of the back-deposition type lithium anode half-cell of the example of the present invention is significantly greater than that of the comparative example, and the capacity curve of the example of the present invention is more gentle as the number of cycles increases. This is because when the equivalent aperture of the ion penetration through hole is too large, the unit deposition amount of lithium ions on the back surface of the metal negative electrode part is small, resulting in a decrease in the battery depositability capacity.
The specific embodiments of the present invention are not intended to be limiting of the invention. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.

Claims (31)

1. A back deposition type metal cathode is characterized by comprising a nonporous electronic insulation layer and two metal cathode parts, wherein each metal cathode part comprises a cathode current collecting layer and a porous electronic insulation layer compounded on one side of the cathode current collecting layer, the cathode current collecting layers of the two metal cathode parts are oppositely arranged, the nonporous electronic insulation layer is arranged between the two metal cathode parts and used for preventing ions from penetrating and electrically insulating, a deposition cavity is formed between the metal cathode parts and the nonporous electronic insulation layer, ion penetrating through holes for the ions to penetrate are arranged at corresponding positions on the porous electronic insulation layer and the cathode current collecting layer, so that the ions can penetrate through the ion penetrating through holes and are deposited into a metal layer on the surface of the non-contact side of the cathode current collecting layer and the porous electronic insulation layer through electrochemical reduction reaction, and the area of the ion penetrating through hole of the porous electronic insulating layer is less than or equal to the area of the ion penetrating through hole of the negative current collecting layer.
2. The metal negative electrode of claim 1, wherein the deposition chamber is a deposition space capable of accommodating deposition of the metal negative electrode, and has a thickness of 0.1mm to 2 mm.
3. The negative back-deposited metal electrode of claim 2, wherein the deposition chamber has a thickness of 0.5mm to 1.5 mm.
4. The reverse deposition type metal anode of claim 2, wherein an insulating support member is provided in the deposition chamber to maintain a deposition space between the metal anode portion and the non-porous electron insulating layer.
5. The reverse deposition-type metal anode of claim 4, wherein the insulating support component comprises one or more of a gasket, a strip-shaped wavy member, a porous insulating material layer and a porous sheet with a convex part on the surface.
6. The metal negative electrode of claim 5, wherein the material of the porous insulating material layer comprises a porous insulating polymer material, a porous insulating inorganic non-metal material, a porous insulating composite material formed by compounding an insulating inorganic non-metal material and an organic polymer material, and the porosity of any one of the porous materials is 30-90%; the porous insulating polymer material is one or more selected from natural cotton and linen, terylene, aramid fiber, nylon, polyolefin, polytetrafluoroethylene and polyvinylidene fluoride, the insulating inorganic non-metallic material is one or more selected from glass fiber cloth and ceramic fiber paper type porous insulating inorganic non-metallic material or one or more selected from silicon oxide, silicon nitride, aluminum oxide and aluminum nitride, and the organic polymer material in the porous insulating composite material is one or more selected from terylene, aramid fiber, nylon, polyolefin, polytetrafluoroethylene and polyvinylidene fluoride.
7. The reverse deposition type metal negative electrode according to claim 1, wherein an equivalent aperture of the ion penetration through hole of the negative current collecting layer of the metal negative electrode part is 0.2mm to 5 mm; the center distance of the holes is 0.5 mm-8 mm; the porosity is 5-70%.
8. The reverse deposition type metal negative electrode according to claim 7, wherein an equivalent aperture of the ion penetration through hole of the negative current collecting layer of the metal negative electrode part is 0.4mm to 2.5 mm.
9. The reverse deposition type metal negative electrode according to claim 7, wherein an equivalent aperture of the ion penetration through hole of the negative current collecting layer of the metal negative electrode part is 0.6mm to 1.8 mm.
10. The reverse deposition metal anode of claim 7, wherein the porosity is 30% to 60%.
11. The reverse deposition metal anode of claim 7, wherein the porosity is from 40% to 50%.
12. The reverse deposition type metal negative electrode according to claim 1, wherein the equivalent aperture of the ion-penetrating through hole of the porous electron insulating layer of the metal negative electrode part is 0.1mm to 5 mm; the center distance of the holes is 0.5 mm-8 mm; the porosity is 5-70%.
13. The reverse deposition type metal negative electrode according to claim 12, wherein the equivalent aperture of the ion penetrating through hole of the porous electron insulating layer of the metal negative electrode part is 0.2mm to 2.5 mm.
14. The reverse deposition type metal negative electrode according to claim 12, wherein the equivalent aperture of the ion penetrating through hole of the porous electron insulating layer of the metal negative electrode part is 0.4mm to 1.8 mm.
15. The reverse deposition metal anode of claim 12, wherein the porosity is 30% to 60%.
16. The reverse deposition metal anode of claim 12, wherein the porosity is from 40% to 50%.
17. The reverse deposition type metal anode of claim 7 or 12, wherein the shape of the ion penetration through hole comprises one or more of a circle, an elliptical hole and a polygon.
18. The reverse deposition metal anode of claim 1, wherein the porous electron insulating layer of the metal anode portion is further composited on sidewalls of ion-penetrating through holes of the anode current collector layer.
19. The metal negative electrode of claim 18, wherein the porous electron insulating layer is tightly combined with one side of the negative current collecting layer and the side wall of the ion through hole thereof by one or more of bonding, coating and mechanical pressing.
20. The reverse deposition-type metal negative electrode of claim 1, wherein the porous electron insulating layer of the metal negative electrode portion is an inorganic material or an organic material capable of shielding ions and electrons from passing therethrough; the organic material is one or more selected from polyimide, polyolefin, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyamide and styrene butadiene rubber; the thickness of the porous electronic insulating layer is 5-500 mu m.
21. The reverse deposition metal anode of claim 20, wherein the porous electron insulating layer has a thickness of 10 to 200 μ ι η.
22. The reverse deposition metal anode of claim 20, wherein the porous electron insulating layer has a thickness of 15 μ ι η to 50 μ ι η.
23. The reverse deposition type metal anode of claim 1, wherein the anode current collecting layer is an electron conducting layer with a thickness of 0.01-2000 μm;
the electronic conducting layer is one or more of foil-shaped, plate-shaped, net-shaped, sheet-shaped and porous foam-shaped conducting metal layers; the conductive metal layer is made of one or more materials selected from lithium, zinc, magnesium, sodium, potassium, calcium, aluminum, iron, stainless steel, nickel, titanium, tin, copper, tin-plated copper and nickel-plated copper;
or the electronic conducting layer is carbon fiber conducting cloth or metal wire and organic fiber mixed conducting cloth; the metal wire is made of one or more of lithium, zinc, magnesium, sodium, potassium, calcium, aluminum, iron, stainless steel, nickel, titanium, tin, copper, tin-plated copper and nickel-plated copper, and the organic fiber wire is one or more of natural cotton hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene;
or the electronic conducting layer is one or more of a conducting metal layer, a conducting cloth, an inorganic non-metallic material and a porous organic material, the surface of which is compounded with a negative conducting particle layer or a metal film; the negative electrode conductive particle layer is a conductive agent or a mixture or a compound of the conductive agent and a negative electrode active material, the conductive agent is one or more selected from carbon black, graphene, carbon nanotubes, carbon fibers, amorphous carbon, metal conductive particles and metal conductive fibers, and the metal conductive particles or the metal conductive fibers are one or more selected from aluminum, stainless steel and silver; the metal film is one or more selected from lithium, zinc, magnesium, sodium, potassium, calcium, aluminum, iron, stainless steel, nickel, titanium, tin, copper, tin-plated copper and nickel-plated copper; the inorganic non-metallic material is one or more selected from glass fiber non-woven fabrics and ceramic fiber paper; the porous organic material is one or more selected from natural cotton and hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene.
24. The reverse deposition metal anode of claim 23, wherein the anode current collector layer is an electronically conductive layer having a thickness of 0.05 μ ι η to 1000 μ ι η.
25. The negative back-deposited metal electrode of claim 1, wherein the non-porous electronically insulating layer is resistant to electrolyte corrosion and electrochemically stable, and is an inorganic or organic material capable of shielding ions and electrons from passing through; the organic material is one or more selected from polyimide, polyolefin, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyamide and styrene butadiene rubber; the thickness of the nonporous electronic insulation layer is 5-1000 μm.
26. The reverse deposition metal anode of claim 25, wherein the non-porous electron insulating layer has a thickness of 10 μ ι η to 300 μ ι η.
27. The reverse deposition metal anode of claim 25, wherein the non-porous electron insulating layer has a thickness of 20 μ ι η to 100 μ ι η.
28. The reverse deposition metal anode of claim 25, wherein the morphology of the non-porous electronically insulating layer comprises one or more of a non-porous film, a sheet, and a sheet.
29. The reverse deposition-type metal anode of claim 28, wherein the non-porous electron insulating layer has blind holes or a rough surface.
30. The reverse deposition metal anode of claim 1, wherein the ions comprise Li+、Zn2+、Mg2+、Na+、K+、Ca2+、Al3+、Fe2+One or more of them.
31. A back-deposited metal negative battery, wherein the back-deposited metal negative battery comprises a cell, an electrolyte, a battery case, a positive terminal and a negative terminal; the battery core comprises a positive plate, an isolation layer and the negative metal electrode of any one of claims 1 to 30, wherein a plurality of the positive plates and a plurality of the negative metal electrodes are alternately stacked, and the isolation layer is arranged between the positive plate and the negative metal electrodes.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237037A (en) * 2007-11-21 2008-08-06 清华大学 Method for making negative pole of lithium ion battery with compound structure via electric sediment technology
CN106299246A (en) * 2016-09-20 2017-01-04 中国科学院化学研究所 Metal secondary batteries composite negative pole and application thereof
CN106702441A (en) * 2016-12-19 2017-05-24 天齐锂业股份有限公司 Method for preparing lithium strip by means of continuous electrodeposition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9705124B2 (en) * 2012-02-27 2017-07-11 The Johns Hopkins University High energy density Li-ion battery electrode materials and cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237037A (en) * 2007-11-21 2008-08-06 清华大学 Method for making negative pole of lithium ion battery with compound structure via electric sediment technology
CN106299246A (en) * 2016-09-20 2017-01-04 中国科学院化学研究所 Metal secondary batteries composite negative pole and application thereof
CN106702441A (en) * 2016-12-19 2017-05-24 天齐锂业股份有限公司 Method for preparing lithium strip by means of continuous electrodeposition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries";Xin-Bing Cheng 等;《Adv. Mater.》;20160222;第28卷;第2888-2895页 *

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