CN108242530B - Lithium slurry battery and negative plate thereof - Google Patents
Lithium slurry battery and negative plate thereof Download PDFInfo
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- CN108242530B CN108242530B CN201611202373.2A CN201611202373A CN108242530B CN 108242530 B CN108242530 B CN 108242530B CN 201611202373 A CN201611202373 A CN 201611202373A CN 108242530 B CN108242530 B CN 108242530B
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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
Abstract
The invention provides a negative plate of a lithium slurry battery, which comprises: the lithium-containing metal body, the embeddable lithium foil layer and the leakage-proof isolation layer form a sandwich composite structure, and the peripheral edge of the sandwich composite structure is insulated and sealed. The lithium-embeddable foil layer can be pulverized in situ to form a lithium-embeddable porous layer in the charging and discharging processes of the lithium slurry battery, and the lithium-embeddable porous layer can avoid the formation of lithium dendrites on the surface of a lithium-containing metal body; furthermore, the pulverized portion of the lithium embeddable foil layer can reduce the true current density of the electrode by increasing the surface area of the material, which can also avoid the formation of lithium dendrites on the surface of the lithium-containing metal. In addition, the lithium-embeddable porous layer is formed in situ in the battery, and the process of additionally preparing the porous lithium-embeddable layer is not needed, so that the preparation process of the pole piece can be effectively simplified, the cost is saved, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical power batteries, and particularly relates to a lithium slurry battery and a negative plate thereof.
Background
Lithium ion batteries are novel high-energy batteries using lithium intercalation compounds as positive and negative electrode materials, and have a series of advantages of high specific energy, high voltage, small self-discharge, good cycle performance, long service life and the like compared with lead-acid batteries and nickel-hydrogen batteries, and are receiving more and more attention. In recent years, lithium ion battery technology has been rapidly developed and has begun to be applied to electric vehicles.
The lithium slurry battery comprises an electrode plate and electrolyte, conductive slurry is formed inside a positive plate and/or a negative plate of the battery after the electrolyte is injected, and the conductive slurry contains conductive particles which are suspended or precipitated in the electrolyte in a certain proportion. When the battery is subjected to external impact or vibration, the part of the conductive particles can move in the electrolyte and form a dynamic conductive network because the part of the conductive particles is not bonded and fixed. The conductive particles are one or a mixture of more of conductive agents such as carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers or metal conductive particles, or the conductive particles are a compound or a mixture of an electrode active material and the conductive agents, and the compound or the mixture comprises surface coating, bonding or mechanical mixing and the like.
In the lithium slurry battery mentioned in chinese invention patent CN201610074921.1, the electronically conductive negative current collector is close to the isolation layer of the battery, so that the lithium ions are easily deposited on the surface of the negative current collector during the large-rate charge and discharge and overcharge of the battery, and there is a risk that "lithium dendrite" pierces the isolation layer and causes short circuit inside the battery. Chinese patent CN201610621508.2 proposes to prevent lithium from depositing on the surface of the lithium-containing metal body to form lithium dendrite by disposing a porous lithium-embeddable current collecting layer between the isolating layer and the lithium-containing metal body, thereby improving the safety of the battery. However, an additional process for preparing a porous lithium-intercalatable current collecting layer is required, and thus the manufacturing cost is high.
Disclosure of Invention
In view of the above problems, the present invention provides a negative electrode sheet for a lithium paste battery. The negative plate comprises a lithium-containing metal body, a lithium-embeddable foil layer and a leakage-proof isolation layer. The lithium-embeddable foil layer can be in-situ pulverized into a lithium-embeddable porous layer through the lithium ion embedding and extracting reaction in the previous several charging and discharging processes of the battery, and the lithium-embeddable porous layer can avoid the formation of lithium dendrites on the surface of a lithium-containing metal body; in addition, the pulverized portion of the lithium embeddable foil layer can reduce the true current density of the electrode due to the increased surface area of the material, which can also avoid the formation of lithium dendrites on the surface of the lithium-containing metal layer, thereby increasing the safety of the battery. In addition, the lithium-embeddable porous layer is formed in situ in the battery, and the process of additionally preparing the porous lithium-embeddable layer is not needed, so that the preparation process of the pole piece can be effectively simplified, the cost is saved, and the production efficiency is improved. In addition, the lithium-containing metal body is simultaneously used as a negative electrode active material and a lithium source, so that the SEI film formation of a negative electrode and the consumption of the lithium of a positive electrode by side reaction in the battery circulation process can be effectively supplemented.
The technical scheme provided by the invention is as follows:
according to the present invention, there is provided a negative electrode sheet for a lithium paste battery, the negative electrode sheet comprising: the lithium-containing metal body, the embeddable lithium foil layer and the leakage-proof isolation layer form a sandwich composite structure, and the peripheral edge of the sandwich composite structure is insulated and sealed. The lithium-embeddable foil layer can be pulverized in situ to form a lithium-embeddable porous layer during charging and discharging of the lithium paste battery. Wherein, the in-situ pulverization of the lithium-embeddable foil layer to form the lithium-embeddable porous layer is realized by the following steps: during several previous charging and discharging processes of the lithium paste battery, intercalation and deintercalation reactions of lithium ions in the material of the lithium intercalatable foil layer cause the lithium intercalatable foil layer to be pulverized in situ to form the lithium intercalatable porous layer.
The lithium-containing metal body may have a single-layer structure or a multi-layer structure, and the material of the lithium-containing metal body may be metallic lithium or a lithium-based alloy. The lithium-based alloy can be Li-Al, Li-Si, Li-Mg, Li-Sn, Li-Bi, Li-Sb, etc., can be binary, ternary or multicomponent alloy, and can include Mg, Ca, Al, Si, Ge, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn, Cd, Hg, etc. elements capable of carrying out solid solution and/or addition reaction with lithium, wherein the content of non-lithium elements is not more than 50%. In the case where the lithium-containing metal body is a multilayer structure, the materials of the respective layers may be the same or may be different. The lithium-containing metal body can be fixed to the current collector layer and/or the lithium-embeddable foil layer by welding, spraying, bonding, electrochemical plating, electroless plating, or mechanical pressing.
The two sides of the lithium-containing metal body are respectively provided with a lithium-embeddable foil layer. The material of the lithium-embeddable foil layer is a material which can carry out reversible lithium-embeddable reaction, has obvious volume change in the lithium-embeddable process and is easy to pulverize in situ. The material of the lithium embeddable foil layer may include: aluminum and aluminum-based alloys, tin and tin-based alloys, zinc and zinc-based alloys, silicon and silicon-based alloys, and the like, which contain elements capable of undergoing a solid solution and/or addition reaction with lithium, such As Mg, Ca, Si, Ge, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn, Cd, Hg, and the like. The thickness of the lithium embeddable foil layer is 0.01 [ mu ] m to 1000 [ mu ] m, preferably 5 [ mu ] m to 200 [ mu ] m, and each lithium embeddable foil layer may be a single-layer structure or a multi-layer structure. In the case where the lithium-embeddable foil layer is a multilayer structure, the materials of the respective layers may be the same or different. The layers in the multilayer structure can be merely stacked together or can be joined together by welding, spraying, bonding, electrochemical plating, electroless plating, vacuum vapor deposition, or mechanical pressing. In addition, the lithium-embeddable foil layer can be bonded to the lithium-containing metal body and/or the current collecting layer by a binder, so that the pulverized flaky or powdery lithium-embeddable material is still bonded to the lithium-containing metal body and is not easy to fall off, and the electric connection performance of the flaky or powdery lithium-embeddable material and the lithium-embeddable porous layer obtained by pulverizing the lithium-embeddable foil layer can be further ensured.
The process of in-situ powdering the lithium intercalatable foil layer into the lithium intercalatable porous layer during charge and discharge will be described in detail below. When the lithium slurry battery is charged and discharged for several times, in the charging process, lithium ions obtain electrons on the surface of the lithium embeddable foil layer and are embedded or deposited into the material of the lithium embeddable foil layer and generate solid solution and/or addition reaction with the material of the lithium embeddable foil layer; during discharge, lithium undergoing a solid solution and/or addition reaction is extracted from the material of the lithium-intercalatable foil layer. Because the volume change of materials such as aluminum and aluminum-based alloy, tin and tin-based alloy, zinc and zinc-based alloy, silicon and silicon-based alloy and the like before and after the lithium intercalation and lithium deintercalation reaction is large, the pulverization of the lithium intercalation layer is caused, and the lithium intercalation porous layer is formed. The lithium-embeddable porous layer continues to be electrically connected to the current collector layer and/or the lithium-containing metal body under the action of cell assembly pressure, a binder, and the like. When the lithium slurry battery is charged and discharged at a large current and overcharged, the lithium-embeddable porous layer can effectively reduce the current density of the electrode and reduce the polarization of the battery under the same apparent area and apparent current; in addition, the growth of lithium dendrite can be stopped by the rheological action of the pulverized lithium-embeddable material partially entering the electrolyte in the negative plate in the electrolyte, so the formation of lithium dendrite on the surface of the lithium-containing metal can be effectively avoided, and the safety of the battery is improved.
The leakage-proof isolation layers positioned at the outermost sides can also be of a single-layer structure or a multi-layer structure. The materials, thicknesses, pore sizes, and porosities of the layers in the multilayer structure may be the same or different. The material of the leakage-proof isolating layer can be an electronic non-conducting porous polymer material; or the material of the leak-proof isolation layer can be a porous material compounded by an electronic non-conductive inorganic non-metallic material and an organic polymer; or the material of the leakage-proof isolation layer can be a gel polymer electrolyte composite material formed by compounding an electronic non-conductive polymer matrix, a liquid organic plasticizer and lithium salt; alternatively, the material of the leakage-proof isolation layer can be an electrolyte or a polymer colloid material which is impregnated with ion conduction in the pores of the porous polymer material which is not electronically conductive or the porous material which is compounded by the inorganic non-metallic material and the organic polymer. The leakage-proof isolating layer plays a role in isolating electrons and preventing the pulverized lithium-embeddable material from leaking from the negative electrode sheet. Preferably, the pore diameter of the leakproof isolation layer is 10-800 μm, the thickness is 0.01-1000 μm, and the porosity of the through hole is 10-90%.
The leakage-proof isolation layer, the lithium-embeddable foil layer, the lithium-containing metal body, the other lithium-embeddable foil layer and the other leakage-proof isolation layer form a sandwich composite structure. The peripheral edge of the sandwich composite structure can realize insulation sealing through the adhesion of the leakage-proof isolation layers positioned at the two outermost sides. It should be noted here that the leakage-proof isolation and insulation sealing of the negative electrode sheet may also be achieved by winding and pasting a single leakage-proof isolation layer at the edge. In addition, the sandwich composite structure can realize insulation sealing through an insulation sealing frame arranged at the peripheral edge of the sandwich composite structure. The insulating sealing frame can be connected to the sandwich composite structure in a hot pressing or sticking mode. The insulating sealing frame can be made of an insulating electrolyte-resistant polymer material, and the insulating electrolyte-resistant polymer material is one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyester terephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene butadiene rubber, sodium carboxymethylcellulose and modified polyolefin.
The negative electrode sheet may further include one or more current collector layers. The current collector layer may be disposed in one or more of the following locations: between two layers in the multilayer structure of the lithium-containing metal body, between the lithium-containing metal body and the lithium embeddable foil layer, and between two layers in the multilayer structure of the lithium embeddable foil layer. In other words, the current collecting layer may be disposed between two layers in the multilayer structure of the lithium-containing metal body and/or both sides of the lithium-containing metal body and/or between two layers in the multilayer structure of the lithium-embeddable foil layer. The current collecting layer can be a conductive metal layer, the conductive metal layer is a metal net or a metal wire mesh grid, and meshes are square, rhombic, rectangular or polygonal; alternatively, the conductive metal layer may be a porous foam metal layer having a porous structure; or the conductive metal layer is formed by mechanical stamping or chemical corrosion of a metal plate or a metal foil; alternatively, when the current collecting layer is disposed in the middle of the multilayer structure of the lithium-containing metal body, the conductive metal layer may also be a metal plate or a metal foil. The conductive metal layer is made of stainless steel, nickel, titanium, silver, tin-plated copper or nickel-plated copper. In addition, the current collecting layer can be carbon fiber conductive cloth, metal wire and organic fiber mixed conductive cloth. In addition, the current collecting layer may be a porous organic material with a conductive coating or a metal film coated on the surface, and the porous organic material includes natural cotton, hemp, terylene, aramid, nylon, polypropylene, polyethylene, polytetrafluoroethylene, and the like.
The negative plate can also be provided with a negative pole tab. The negative pole tab can be electrically connected with the lithium-containing metal body; or the negative pole tab can be electrically connected with the current collecting layer; alternatively, the negative electrode tab may be electrically connected to the lithium-containing metal body and to the current collecting layer. That is, both the current collector layer and the lithium-containing metal body can function as current collectors. When the current collecting layer and the lithium-containing metal body simultaneously collect current, the current collecting effect is uniform, and the situations of heating and the like caused by high-rate charge and discharge can be avoided.
According to the present invention, there is provided a lithium paste battery including: the negative plate of the lithium slurry battery, the positive plate of the lithium slurry battery, the battery shell, the positive terminal, the negative terminal, the liquid injection port and the electrolyte are arranged in the battery shell, wherein the negative plate and the positive plate are crossed and superposed to form a battery cell, and the battery cell is arranged in the battery shell. The positive electrode tab of the battery cell is electrically connected to the positive terminal, and the negative electrode tab of the battery cell is electrically connected to the negative terminal. The positive terminal and the negative terminal extend out of the battery shell and are in fluid sealing with the battery shell, and electrolyte is injected into the battery shell through the liquid injection port so that the battery core is placed in the electrolyte.
The positive plate of the lithium slurry battery can be a sandwich composite positive plate. The structure of the sandwich composite positive electrode sheet is given by way of example to facilitate a better understanding of the present invention. The sandwich composite positive plate can comprise a porous current-collecting positive plate layer and positive slurry, wherein the porous current-collecting positive plate layer is formed by coating a porous positive material layer on one side or two sides of a porous positive current collector, the positive slurry with the thickness of 0-5 mm is filled between the two porous current-collecting positive plates, and part or all of the positive slurry permeates into pores of the porous current-collecting positive plates to form the sandwich composite positive plate; and the periphery of the sandwich composite positive plate is provided with an insulating sealing frame which is in a shape of a 'return' and is fixedly sealed with the edge of the porous current-collecting positive plate, so that the positive slurry is prevented from leaking from four sides of the sandwich composite positive plate. It should be noted that the positive electrode sheet herein may be any positive electrode sheet for a lithium paste battery, and the structure thereof is not limited to the above-described examples.
The positive electrode slurry can comprise electrolyte and positive electrode conductive particles capable of flowing in the electrolyte, wherein the positive electrode conductive particles account for 5-80% of the positive electrode slurry by mass, and the average particle size is 0.5-500 μm. The positive conductive particles can be one or more of carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers, various metal conductive particles and other conductive agents, and the composite mode comprises surface coating, bonding or mechanical mixing and the like; or the positive conductive particles can be a compound or a mixture of a positive active material and the various conductive agents, wherein the mass ratio of the positive active material to the conductive agents is 0-98: 100-2, the compounding or mixing method comprises surface coating, bonding or mechanical mixing and the like. The positive active material is one or more of 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 and lithium iron nickel manganese oxides.
It should be noted that the positive electrode sheet herein may be any positive electrode sheet for a lithium paste battery, and the structure and material thereof are not limited to the above examples.
The invention has the advantages that:
(1) the lithium-embeddable foil layer in the lithium slurry battery negative plate can be pulverized in situ to form a lithium-embeddable porous layer during charging and discharging without additionally preparing the porous lithium-embeddable layer, so that the preparation process of the negative plate can be effectively simplified, the cost is saved, and the production efficiency is improved;
(2) the lithium embeddable porous layer formed by in-situ pulverization can effectively reduce the current density of the electrode and reduce the polarization of the battery, and can prevent the growth of lithium dendrite through the rheological action of the non-bonding fixed part of the pulverized granular material of the lithium embeddable porous layer in the electrolyte in the negative plate, thereby effectively avoiding the formation of the lithium dendrite on the surface of the lithium-containing metal body, and further increasing the safety of the battery;
(3) the lithium-containing metal body in the negative plate of the lithium slurry battery is simultaneously used as a negative active material and a lithium source, so that the SEI film formation of the negative electrode and the lithium consumption caused by side reactions in the battery circulation process can be effectively supplemented, and the energy density of the battery is improved and the circulation performance is improved.
Drawings
Fig. 1 is a schematic diagram of a lithium paste battery of the present invention;
FIG. 2 is a schematic diagram of in-situ pulverization of a lithium embeddable foil layer according to the present disclosure, wherein FIG. 2(a) is a schematic diagram of a lithium ion and a lithium embeddable foil layer that is not embedded with lithium ions; FIG. 2(b) is a schematic view of lithium ions being inserted into a lithium embeddable foil layer; FIG. 2(c) is a schematic illustration of in situ pulverization of a lithium-intercalatable foil layer to form a lithium-intercalatable porous layer;
fig. 3 is a charge-discharge curve diagram of a lithium slurry battery, wherein in fig. 3(a), the positive electrode material of the battery is lithium iron phosphate slurry, the negative electrode is metal lithium, and the lithium-embeddable foil layer is an aluminum foil; in fig. 3(b), the positive electrode material of the battery is lithium iron phosphate slurry, the negative electrode only includes a lithium embeddable foil layer, and the lithium embeddable foil layer is aluminum foil;
fig. 4 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to an embodiment of the present invention;
fig. 5 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to another embodiment of the present invention.
List of reference numerals
1-sandwich composite positive plate
101-porous current collecting positive electrode layer
102-positive electrode paste
2-negative plate
201. 201' -isolation layer
202. 202' -lithium embeddable foil layer
203. 203' -lithium-containing metal bodies
204-sandwich composite structure
205. 205' -current collecting layer
206' -insulating sealing frame
3-isolating Chamber
Detailed Description
The invention will be further explained by embodiments in conjunction with the drawings.
Fig. 1 is a schematic view of a lithium paste battery according to the present invention. The battery core of the lithium slurry battery comprises a plurality of sandwich composite positive plates 1 and negative plates 2 which are alternately arranged, an isolation cavity 3 with the height of 0.1-1 mm is arranged between the sandwich composite positive plates 1 and the negative plates 2, and the isolation cavity 3 is filled with electrolyte. The sandwich composite positive plate 1 comprises a porous current collecting positive layer 101 and positive slurry 102, wherein the porous current collecting positive layer 101 is formed by coating a porous positive material layer on one side or two sides of a porous positive current collector, the positive slurry 102 with the thickness of 0-5 mm is filled between the two porous current collecting positive layers 101, and part or all of the positive slurry 102 permeates into pores of the porous current collecting positive layers 101 to form the sandwich composite positive plate 1. The negative plate 2 comprises a leakage-proof isolation layer 201, a lithium-embeddable foil layer 202 and a lithium-containing metal body 203, wherein the leakage-proof isolation layer 201, the lithium-embeddable foil layer 202 and the lithium-containing metal body 203 form a sandwich composite structure 204. When the battery is overcharged or rapidly charged with large multiplying power, a large amount of lithium ions are not deposited on the surface of the lithium-containing metal body 203, but are embedded into the lithium-embeddable foil layer 202, so that lithium dendrite is prevented from being formed on the surface of the lithium-containing metal body; in addition, the lithium-containing metal body 203 can supplement the consumption of lithium ions caused by the negative SEI film formation during the charge and discharge process of the battery, particularly during the first charge.
Fig. 2 is a schematic diagram of in-situ pulverization of a lithium-embeddable foil layer in accordance with the present invention. Wherein, fig. 2(a) is a schematic view of lithium ions and lithium embeddable foil layers in which lithium ions are not embedded; FIG. 2(b) is a schematic view of lithium ions being inserted into a lithium embeddable foil layer; FIG. 2(c) is a schematic diagram of in situ pulverization of a lithium-intercalatable foil layer to form a lithium-intercalatable porous layer. Next, the process of in-situ pulverization of the lithium intercalatable foil layer to form the lithium intercalatable porous layer will be described. Here, the material of the lithium embeddable foil layer is exemplified by aluminum. In the charging process, lithium ions obtain electrons on the surface of the lithium embeddable foil layer to be embedded or deposited into the material of the lithium embeddable foil layer and generate solid solution or addition reaction with aluminum atoms in the lithium embeddable foil layer; during discharge, lithium undergoing a solid solution or addition reaction is extracted from the material of the lithium-intercalatable foil layer. Since the volume change of aluminum before and after the lithium intercalation and lithium deintercalation reaction is large, the lithium intercalation material capable of intercalating the lithium foil layer is pulverized, so that a lithium intercalation porous layer and a pulverized material in a powder or a sheet shape are formed. The powdered or flake-like pulverized material may be partly bonded to the lithium-containing metal body and/or the current collecting layer by a binder, and partly may enter the electrolyte in the negative electrode sheet. The powdered material bonded to the metal body and/or current collector layer may continue to remain electrically connected to the current collector layer and/or lithium-containing metal body and may be able to continue the reactions of lithium deintercalation. The powdery or flaky powdered material entering the electrolyte in the negative electrode slice can also play a role in inhibiting the growth of lithium dendrites under the rheological action of the electrolyte.
Fig. 3 is a charge-discharge curve diagram of a lithium slurry battery, wherein in fig. 3(a), the positive electrode material of the battery is lithium iron phosphate slurry, the negative electrode is metal lithium, and the lithium-embeddable foil layer is an aluminum foil; in fig. 3(b), the positive electrode material of the battery is lithium iron phosphate slurry, the negative electrode only includes a lithium embeddable foil layer, and the lithium embeddable foil layer is aluminum foil. Fig. 3(a) shows that two charging platforms appear during the first charging process, and therefore, it can be seen that lithium intercalation alloying (2.85V) is completed during the first charging and discharging, lithium ions are not blocked from passing through, and the battery is subsequently represented by the charging and discharging reaction of lithium iron phosphate to metallic lithium. In FIG. 3(b), the potential of the lithium intercalation alloying reaction occurring during charge and discharge of the aluminum foil was 3.28V, and the potential of lithium deintercalation was 2.85V. As can be seen from the graph, the battery performance was poor in the case where the negative electrode included only the aluminum foil, because the pulverization was severe after the alloying reaction of the aluminum material and the capacity was rapidly attenuated.
Fig. 4 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to an embodiment of the present invention. The negative electrode sheet includes a single-layered lithium-containing metal body 203. Current collecting layers 205 are provided on both sides of the lithium-containing metal body 203. The lithium-containing metal body is fixed to the current collector layer by welding. A lithium embeddable foil layer 202 is provided on the side of the current collecting layer 205 that is not in contact with the lithium-containing metal body 203. The lithium embeddable foil layer 202 may be bonded to the current collector layer 205 by a conductive adhesive. During the first few charges and discharges of the lithium paste battery, lithium ions are intercalated and deintercalated in lithium-intercalatable foil layer 202 and cause the lithium-intercalatable foil layer to be pulverized into a lithium-intercalatable porous layer in situ. The lithium-intercalatable porous layer can allow lithium ions to pass smoothly, and can also allow lithium ions to be intercalated into the lithium-intercalatable material thereof under the condition of overcharge or high-rate quick charge. In this way, the lithium ion intercalation reaction occurring on the negative electrode does not become deposition of lithium ions on the surface of the lithium-containing metal body, and therefore formation of lithium dendrites on the surface of the lithium-containing metal body is avoided. The outer side of the lithium-embeddable foil layer 202 is provided with a leakage-proof isolation layer 201, and the end parts of the two leakage-proof isolation layers 201 are connected together in a sticking way so as to form the insulation seal of the peripheral edge of the negative plate. The pulverized lithium-embeddable material of the lithium-embeddable foil layer 202 partially adheres to the current collector layer 205 and partially enters the electrolyte inside the negative electrode sheet, and the leakage-preventing separator layer 201 can prevent the pulverized lithium-embeddable material from leaking into the electrolyte outside the negative electrode sheet.
Fig. 5 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to another embodiment of the present invention. The negative electrode sheet includes a lithium-containing metal body 203' having a two-layer structure. A current collecting layer 205 'is provided between the two-layer structure of the lithium-containing metal body 203'. The lithium-containing metal body is fixed to the current collector layer by means of adhesion. A lithium embeddable foil layer 202' having a two-layer structure is provided on the side of the lithium-containing metal body 203' not in contact with the current collector layer 205 '. The two-layer structure of the lithium embeddable foil layer 202' has different thicknesses and is bonded together by a conductive adhesive. The lithium embeddable foil layer 202 'may be bonded to the lithium-containing metal body 203' by a conductive adhesive. During the first few charging processes of the lithium paste battery, lithium ions are intercalated and deintercalated in the lithium intercalatable foil layer and the lithium intercalatable foil layer is pulverized into the lithium intercalatable porous layer in situ. The lithium-intercalatable porous layer can allow lithium ions to pass smoothly, and can also allow lithium ions to be intercalated into the lithium-intercalatable material thereof under the condition of overcharge or high-rate quick charge. In this way, the lithium ion intercalation reaction occurring on the negative electrode does not become deposition of lithium ions on the surface of the lithium-containing metal body, and therefore formation of lithium dendrites on the surface of the lithium-containing metal body is avoided. The outer side of the lithium embeddable foil layer 202 'is provided with a leakage-proof isolation layer 201'. The entire sandwich composite structure is hermetically connected by an insulating sealing frame 206'. The pulverized lithium-embeddable material of the lithium-embeddable foil layer 202 'is partially adhered to the lithium-containing metal body 203' and partially enters the electrolyte inside the negative electrode sheet, and the leakage-proof isolation layer 201 'and the insulating sealing frame 206' can prevent the pulverized lithium-embeddable material from leaking into the electrolyte outside the negative electrode sheet.
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 (15)
1. A negative electrode sheet for a lithium paste battery, comprising: the lithium-containing metal body, the lithium-embeddable foil layers positioned on two sides of the lithium-containing metal body and the leakage-proof isolation layers positioned on the outermost two sides form a sandwich composite structure, and the peripheral edge of the sandwich composite structure is subjected to insulation sealing, wherein the lithium-embeddable foil layers can be pulverized in situ to form a lithium-embeddable porous layer in the charging and discharging processes of the lithium slurry battery, and a process of additionally preparing the porous lithium-embeddable layer is not needed;
the material of the lithium-containing metal body is metal lithium or lithium-based alloy; the material of the lithium embeddable foil layer is a material which can perform reversible lithium-embedding reaction, change volume in the lithium-embedding process and generate in-situ pulverization, and the material of the lithium embeddable foil layer comprises one or more of aluminum and aluminum-based alloy, tin and tin-based alloy, zinc and zinc-based alloy, silicon and silicon-based alloy.
2. The negative electrode sheet for a lithium paste battery according to claim 1, wherein the thickness of the lithium embeddable foil layer is 0.01 to 1000 μm.
3. The negative electrode sheet for a lithium paste battery according to claim 2, wherein the thickness of the lithium embeddable foil layer is 5 μm to 200 μm.
4. The negative electrode sheet of a lithium paste battery according to any one of claims 1 to 3, wherein the lithium-containing metal body, the lithium embeddable foil layer, and the leakage-preventing separator layer each may be a single-layer structure or a multi-layer structure;
in the case of a multilayer structure, the materials and thicknesses of the respective layers in the multilayer structure of the lithium-containing metal body are the same or different; the materials and the thicknesses of all layers in the multilayer structure of the lithium embeddable foil layer are the same or different; the materials, thicknesses, pore diameters and porosities of all layers in the anti-leakage isolating layer are the same or different.
5. The negative electrode sheet for a lithium paste battery according to any one of claims 1 to 3, wherein the peripheral edge of the sandwich composite structure is insulation-sealed by adhesion of the leakage preventing separator layers located at the outermost sides.
6. The negative electrode sheet of the lithium slurry battery according to any one of claims 1 to 3, wherein an insulating sealing frame is arranged at the peripheral edge of the sandwich composite structure, the insulating sealing frame is connected to the sandwich composite structure through hot pressing or pasting, the insulating sealing frame is made of an insulating electrolyte-resistant polymer material, and the insulating electrolyte-resistant polymer material is one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyterephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene butadiene rubber, sodium carboxymethylcellulose and modified polyolefin.
7. The negative electrode sheet for a lithium paste battery according to any one of claims 1 to 3, wherein the material of the leak-proof separator is an electronically nonconductive porous polymer material; or the material of the leakage-proof isolating layer is a porous material compounded by an electronic non-conductive inorganic non-metallic material and an organic polymer; or the material of the leakage-proof isolating layer is a gel polymer electrolyte composite material formed by compounding an electronic non-conductive polymer matrix, a liquid organic plasticizer and lithium salt; or the material of the leakage-proof isolating layer is an electrolyte or a polymer colloid material which is impregnated with ion conduction in the pores of the porous polymer material with non-conductive electrons or the pores of the porous material compounded by the inorganic non-metallic material and the organic polymer.
8. The negative electrode sheet for a lithium paste battery according to any one of claims 1 to 3, wherein the leak-proof separator has a pore diameter of 10 to 800 μm, a thickness of 0.01 to 1000 μm, and a through-hole porosity of 10 to 90%.
9. The negative electrode sheet for a lithium paste battery according to claim 4, wherein the negative electrode sheet further comprises a plurality of current collecting layers disposed between the lithium-containing metal body and the lithium embeddable foil layer and/or between two layers in a multilayer structure of the lithium embeddable foil layer.
10. The negative electrode sheet for a lithium paste battery according to claim 9, wherein the current collecting layer is a conductive metal layer, the conductive metal layer is a metal mesh, and the mesh is polygonal; or the conductive metal layer is a porous foam metal layer with a porous structure; or the conductive metal layer is formed by mechanically stamping or chemically corroding a metal plate or a metal foil, and the conductive metal layer is made of stainless steel, nickel, titanium, silver, tin-plated copper or nickel-plated copper; or
The current collecting layer is carbon fiber conductive cloth, metal wire and organic fiber mixed conductive cloth; or
The current collecting layer is a porous organic material with a surface coated with a conductive coating or plated with a metal film, and the porous organic material comprises one of natural cotton, linen, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene.
11. The negative electrode sheet for a lithium paste battery according to claim 9, wherein the lithium embeddable foil layer is bonded to the lithium-containing metal body and/or to the current collecting layer by a conductive adhesive.
12. The negative electrode sheet for a lithium paste battery according to claim 4, wherein the negative electrode sheet further comprises a current collecting layer disposed between two layers of the multilayer structure of the lithium-containing metal body and/or between the lithium-containing metal body and the lithium embeddable foil layer and/or between two layers of the multilayer structure of the lithium embeddable foil layer.
13. The negative electrode sheet for a lithium paste battery according to claim 12, wherein the current collecting layer is a conductive metal layer, the conductive metal layer is a metal mesh, and meshes are polygonal; or the conductive metal layer is a porous foam metal layer with a porous structure; or the conductive metal layer is formed by mechanically stamping or chemically corroding a metal plate or a metal foil; or the conductive metal layer is a metal plate or a metal foil, and the conductive metal layer is made of stainless steel, nickel, titanium, silver, tin-plated copper or nickel-plated copper; or
The current collecting layer is carbon fiber conductive cloth, metal wire and organic fiber mixed conductive cloth; or
The current collecting layer is a porous organic material with a surface coated with a conductive coating or plated with a metal film, and the porous organic material comprises one of natural cotton, linen, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene.
14. The negative electrode sheet for a lithium paste battery according to any one of claims 9 to 13, wherein the negative electrode sheet is provided with a negative electrode tab that is electrically connected to the lithium-containing metal body; or the negative electrode tab is electrically connected with the current collecting layer; or the negative pole tab is electrically connected with the lithium-containing metal body and the current collecting layer.
15. A lithium paste battery, characterized in that the lithium paste battery comprises: the negative electrode tab of the lithium paste battery, the positive electrode tab of the lithium paste battery, the battery case, the positive electrode terminal, the negative electrode terminal, the electrolyte injection port, and the electrolyte according to any one of claims 1 to 14, wherein the negative electrode tab and the positive electrode tab are stacked in a crossing manner to form a cell, the cell is disposed in the battery case, the positive electrode tab of the cell is electrically connected to the positive electrode terminal, the negative electrode tab of the cell is electrically connected to the negative electrode terminal, the positive electrode terminal and the negative electrode terminal protrude from the battery case and are fluid-tight to the battery case, and the electrolyte is injected into the battery case through the electrolyte injection port so that the cell is disposed in the electrolyte.
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| CN201611202373.2A CN108242530B (en) | 2016-12-23 | 2016-12-23 | Lithium slurry battery and negative plate thereof |
| PCT/CN2017/075925 WO2017152836A1 (en) | 2016-03-08 | 2017-03-08 | Cell for lithium paste battery, and lithium paste battery module |
| US16/082,838 US10868337B2 (en) | 2016-03-08 | 2017-03-08 | Cell-core for lithium slurry battery, and lithium slurry battery module |
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