CN107681115B - Negative plate of lithium slurry battery - Google Patents
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- CN107681115B CN107681115B CN201610621508.2A CN201610621508A CN107681115B CN 107681115 B CN107681115 B CN 107681115B CN 201610621508 A CN201610621508 A CN 201610621508A CN 107681115 B CN107681115 B CN 107681115B
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- 239000002002 slurry Substances 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 102
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative plate of a lithium slurry battery, which comprises an insulating sealing frame, a lithium-containing metal body and an embeddable lithium current collecting structure layer. The lithium-embeddable current collecting structure layer, the lithium-containing metal body and the other lithium-embeddable current collecting structure layer form a sandwich composite structure, the insulating sealing frame seals the peripheral edge of the sandwich composite structure, and the material of the lithium-embeddable current collecting structure layer contains a lithium-embeddable material capable of embedding lithium in the charging and discharging processes of the lithium slurry battery. The lithium-embeddable current collecting structure layer in the negative plate can play a role of embedding lithium during charging, so that lithium is prevented from depositing on the surface of a lithium-containing metal body to form lithium dendrites, and the safety of the battery is improved. In addition, the lithium-containing metal body can also be used as a lithium source, so that the SEI film of the negative electrode can be effectively formed, and the consumption of the lithium of the positive electrode caused by side reaction in the battery circulation process can be effectively supplemented. In addition, the common current collection of the lithium-containing metal body and the lithium-embeddable current collection structure layer ensures that the current collection effect is uniform, and the situations of heating and the like caused by high-rate charge and discharge are avoided.
Description
Technical Field
The invention belongs to the technical field of electrochemical power batteries, and particularly relates to a negative plate of a lithium slurry battery.
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, amorphous carbon 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. In addition, chinese patent CN201510164222.1 proposes a lithium slurry battery with a negative electrode current collector disposed inside the negative electrode reaction cavity, which has the problem that the negative electrode slurry is accompanied by the generation, destruction and repair of SEI film during the first and subsequent cycles, and this process consumes electrolyte and active lithium, resulting in deterioration of the cycle performance of the battery.
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 and a lithium-embeddable current collecting structure layer, wherein the lithium-embeddable current collecting structure layer can play a role of embedding lithium during charging, lithium is prevented from depositing on the surface of the lithium-containing metal body to form lithium dendrites, and the safety of the battery is greatly improved. In addition, the lithium-containing metal body can also be used as a lithium source, so that the SEI film of the negative electrode can be effectively formed, and the consumption of the lithium of the positive electrode caused by side reaction in the battery circulation process can be effectively supplemented. In addition, the common current collection of the lithium-containing metal body and the lithium-embeddable current collection structure layer ensures that the current collection effect is uniform, and the situations of heating and the like caused by high-rate charge and discharge are avoided.
The technical scheme provided by the invention is as follows:
the invention provides a negative plate of a lithium slurry battery, which comprises an insulating sealing frame, a lithium-containing metal body and a lithium-embeddable current collecting structure layer, wherein the lithium-embeddable current collecting structure layer, the lithium-containing metal body and the other lithium-embeddable current collecting structure layer form a sandwich composite structure, and the insulating sealing frame seals the peripheral edge of the sandwich composite structure. The material of the lithium-embeddable current collecting structure layer contains a material which can embed lithium in the charging and discharging process of the lithium slurry battery, namely a lithium-embeddable material. Preferably, the lithium-intercalatable material is a material that reversibly deintercalates lithium during charging, and includes: aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metallic lithium powder, graphite and the like which can be intercalated with lithium.
The lithium-embeddable current collecting structure layer can comprise a current collecting porous part, the thickness of the current collecting porous part is 0.01-2000 mu m, the porosity of a through hole is 30-98%, and the aperture range is 10 nm-2 mm. As described above, the material of the lithium intercalatable current collecting structure layer contains a lithium intercalatable material capable of intercalating lithium during charge and discharge of the lithium paste battery. Specifically, when the lithium-intercalatable current collecting structure layer includes only the current collecting porous portion, the current collecting porous portion needs to contain the above-described lithium-intercalatable material.
The lithium-embeddable current collecting structure layer can also comprise a current collecting porous part and a slurry part at the same time. Depending on the porosity, pore size, and consistency of the slurry in the slurry portion, the slurry portion may be adjacent to the manifold porous portion, or the slurry in the slurry portion may partially or fully infiltrate the pores of the manifold porous portion. The two lithium-embeddable current collecting structure layers are arranged on two sides of the lithium-containing metal body in a mode that the slurry part is adjacent to the lithium-containing metal body. In this way, the collecting porous part of the lithium-embeddable collecting structure layer not only can play a role in embedding lithium and collecting current, but also can play a role in preventing slurry in the slurry part from leaking from the negative plate. The thickness of the manifold porous part is 0.01-2000 mu m, the porosity of the through hole is 30-98%, the aperture range is 10 nm-2 mm, and the thickness of the slurry part is 0-2 mm. When the lithium intercalatable current collecting structure layer includes a current collecting porous portion and a paste portion, the current collecting porous portion and/or the paste portion contains the lithium intercalatable material, and preferably, both the current collecting porous portion and the paste portion contain the lithium intercalatable material. The slurry part may include an electrolyte and conductive lithium-intercalatable particles capable of flowing in the electrolyte, wherein the conductive lithium-intercalatable particles account for 10 to 90% by mass of the slurry part and have an average particle diameter of 500nm to 500 μm. The conductive lithium-intercalatable particles are a compound or a mixture of a lithium-intercalatable material and a conductive agent, wherein the mass ratio of the lithium-intercalatable material to the conductive agent is (0-98): 100-2, the compounding or mixing mode comprises surface coating, bonding or mechanical mixing and the like, and the conductive agent is one or more of carbon black, ketjen black, graphene, carbon nano tubes, carbon fibers, amorphous carbon or metal conductive particles and the like.
The current collecting porous portion may be a single-layer structure or a multi-layer structure. In other words, the manifold porous section may comprise one porous layer or a plurality of porous layers. When the current collecting porous portion includes one porous layer, the porous layer functions both as a lithium intercalation function and as a current collecting function. That is, the material of the porous layer is a lithium intercalation metal conductive material or a conductive material coated with a lithium intercalation material. When the current collecting porous portion includes a plurality of porous layers, the material, thickness, porosity, and pore size of each porous layer may be the same or may be different as long as one of the porous layers can function as a lithium intercalation and one of the porous layers can function as a current collecting. The multiple porous layers may be joined together by welding, spraying, bonding, mechanical pressing, etc. The advantage of having multiple porous layers is that the material, thickness, porosity and pore size of each porous layer can be specifically tailored by the actual needs.
The insulating sealing frame is arranged on the periphery of a sandwich composite structure consisting of a lithium-embeddable current collecting structure layer-a lithium-containing metal body-a lithium-embeddable current collecting structure layer. The insulating sealing frame is connected to the sandwich composite structure in a hot pressing, sticking and other modes. The insulating sealing frame functions as insulation, and, when the lithium-embeddable current collecting structure layer includes the paste portion, the insulating sealing frame also functions as sealing to prevent the paste in the paste portion from leaking from the peripheral edge of the sandwich composite structure. The material of the insulating sealing frame is a polymer material which is insulating and electrolyte-resistant, such as 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, modified polyolefin and the like.
An isolating layer for electronic insulation ion conduction can be arranged on the surface of the negative plate. The material of the isolating layer is an electronic non-conducting porous polymer material, such as: polyethylene, polypropylene, polyvinylidene fluoride, and the like; or, the material of the isolation layer is a composite porous material of an inorganic non-metallic material and an organic polymer, which are not electrically conductive, for example: glass fiber nonwoven fabrics, synthetic fiber nonwoven fabrics, ceramic fiber paper, and the like; or the isolating layer is made of a gel polymer electrolyte composite material formed by compounding an electronic non-conductive polymer matrix, a liquid organic plasticizer and lithium salt; or the isolating layer is made of a porous polymer material which is not electrically conductive by electrons or a composite porous material of an inorganic non-metallic material and an organic polymer, and the pores of the porous polymer material are impregnated with an ion-conductive electrolyte or a polymer colloid material.
The material of the lithium-containing metal body is metallic lithium or a lithium-rich alloy. The lithium-rich alloy includes, for example, an aluminum lithium alloy, a lithium magnesium alloy, a lithium silicon alloy, and the like. When the lithium-embeddable current collecting structure layer includes only the current collecting porous portion, the lithium-containing metal body may be fixed to the current collecting porous portion by welding, spraying, bonding, electrochemical plating, chemical plating, or mechanical press-fitting. When the lithium-embeddable current collecting structure layer comprises a current collecting porous part and a slurry part, the sandwich composite structure of the lithium-embeddable current collecting structure layer, the lithium-containing metal body and the lithium-embeddable current collecting structure layer is fixedly connected through the insulating sealing frame. The lithium-containing metal body can be used as a lithium source to supplement the SEI film formation of the negative electrode and consume the lithium of the positive electrode by side reaction in the battery cycle process.
The negative pole piece is provided with a negative pole tab which can be electrically connected with the current collecting porous part of the lithium current collecting structure layer or the lithium-containing metal body; alternatively, the negative electrode tab may be electrically connected to the current collecting porous portion of the lithium-embeddable current collecting structure layer and to the lithium-containing metal body. That is, both the lithium-intercalatable current collecting structure layer and the lithium-containing metal body may function as current collectors. When the lithium-embeddable current collecting structure 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.
The current collecting porous portion may be a porous lithium-intercalatable metal conductive layer, or may be a porous conductive layer whose surface is coated with a lithium-intercalatable material.
When the current collecting porous part is a porous lithium embeddable metal conducting layer, the porous lithium embeddable metal conducting layer can be a metal net or a metal wire woven net, and meshes are square, rhombic, rectangular or polygonal; or the porous lithium-embeddable metal conducting layer is a porous foam metal layer with a porous structure; or, the porous lithium-embeddable metal conductive layer is formed by mechanically stamping or chemically etching a porous metal plate or a metal foil. The porous lithium-embeddable metal conducting layer is made of aluminum, aluminum lithium alloy, tin-based alloy, lithium silicon alloy and lithium titanium alloy lithium-embeddable metal, and the thickness of the porous lithium-embeddable metal conducting layer is 0.5 mm-1 mm.
When the current collecting porous part is a porous conducting layer coated with a material capable of embedding lithium, the porous conducting layer can be a conducting metal layer, the conducting metal layer is a metal net or a metal wire woven net, and meshes are square, rhombic, rectangular or 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 porous 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 and the like. Or the porous conducting layer can be carbon fiber conducting cloth, metal wire and organic fiber wire mixed conducting cloth, a porous organic material with a conducting coating or a metal film coated on the surface, and the porous organic material comprises natural cotton hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene, polytetrafluoroethylene and other organic matters with good electrolyte resistance. The lithium-embeddable material is one or more of aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metallic lithium powder, graphite and the like which can embed lithium. The lithium embeddable material is attached to the surface of the porous conductive layer by casting, coating, hot rolling, screen printing, ink jet printing, spraying, bonding, electrochemical plating, electroless plating, or mechanical pressing.
In addition, the current collecting porous portion may be a porous mixture of a lithium intercalatable material, a conductive filler and a binder or a porous mixture of a lithium intercalatable material, a conductive filler and a polymer electrolyte layer. The mass fraction of the conductive filler is not less than 70%, and the mass fraction of the lithium-intercalatable material is not less than 10%. Wherein, the lithium-embeddable material is one or more of aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metallic lithium powder, graphite and the like which can embed lithium; the conductive filler is one or more of carbon black, carbon nano tubes, carbon fibers, graphene, titanium powder, aluminum powder, silver powder, alloy aluminum powder, stainless steel powder or silver powder, lithium-rich silicon powder, lithium-containing alloy powder and metal alloy conductive particles, or lithium-containing carbon materials; the binder 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, modified polyolefin and the like; the polymer electrolyte layer is a gel polymer electrolyte composite material formed by compounding a polymer matrix, a liquid organic plasticizer and lithium salt.
The invention has the advantages that:
(1) the lithium-embeddable current collecting structure layer in the lithium slurry battery negative plate can embed lithium during charging, and particularly, when the lithium-embeddable current collecting structure layer comprises a slurry part, the growth of lithium dendritic crystals can be prevented through the rheological action of the slurry, so that the possibility of internal short circuit of the battery caused by lithium depositing on the surface of a lithium-containing metal body during charging and discharging of the battery is greatly reduced;
(2) the lithium-containing metal body in the negative plate of the lithium slurry battery can be used as a lithium source to effectively supplement the negative SEI film formation and the lithium consumption caused by side reaction in the battery circulation process, so that the energy density and the efficiency of the battery are improved;
(3) the current distribution in the negative plate is more uniform under the combined current collecting action of the lithium-containing metal body and the lithium-embeddable current collecting structure layer, and the heating phenomenon caused by the high-rate charge and discharge of the battery is avoided.
Drawings
Fig. 1 is a schematic diagram of a lithium paste battery of the present invention;
fig. 2 is a schematic view of a negative electrode sheet of a lithium paste battery of the present invention;
fig. 3 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to a first embodiment of the present invention;
fig. 4 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to a second 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 a third embodiment of the present invention;
fig. 6 is a charge and discharge test chart of a battery with a negative plate of a lithium plate and a negative plate of a composite structure of an aluminum mesh and the lithium plate under different multiplying powers, wherein the positive electrode is a lithium iron phosphate coated plate, and the negative plate of fig. 6(a) is the lithium plate; the negative electrode plates in fig. 6(b) and (c) are composite structures of aluminum mesh and lithium plate;
fig. 7 is a test chart of the lithium intercalation slurry, and fig. 7(a) is a charge-discharge test of a graphite slurry half cell; FIG. 7(b) shows a battery charge/discharge test in which the positive electrode is a lithium iron phosphate pole piece and the negative electrode is graphite slurry; fig. 7(c) shows a battery charge/discharge test in which the positive electrode is a lithium iron phosphate sheet and the negative electrode is a sheet containing lithium and graphite slurry.
List of reference numerals
1-sandwich composite positive plate
101-porous current collecting positive electrode layer
102-conductive paste
2-negative plate
201-insulating sealing frame
202-lithium embeddable current collecting structure layer
203-negative pole tab
204-manifold porous section
205-lithium-containing metal body
206-slurry section
207-porous layer
208-sandwich composite structure
3-isolating Chamber
4-isolation layer
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 conductive 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 conductive 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 conductive 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 lithium-intercalatable current collecting structure layer 202 and a lithium-containing metal body 205, wherein the lithium-intercalatable current collecting structure layer 202, the lithium-containing metal body 205 and the other lithium-intercalatable current collecting structure layer 202 form a sandwich composite structure 208. 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 205, but are embedded into the lithium-embeddable current collecting structure layer 202, so that lithium dendrites are prevented from being formed on the surface of the negative electrode; in addition, the lithium-containing metal body 205 can supplement the consumption of lithium ions caused by the negative SEI film during the charging and discharging process of the battery, particularly during the first charging; moreover, the lithium-embeddable current collecting structure layer 202 and the lithium-containing metal body 205 can simultaneously play a current collecting role, so that the current collecting effect is better and more uniform, and the situations of heating and the like caused by high-rate charge and discharge are avoided.
Fig. 2 is a schematic perspective view of a negative electrode sheet of a lithium paste battery according to the present invention. The negative plate 2 comprises an insulating sealing frame 201 and a sandwich composite structure 208 formed by a lithium-embeddable current collecting structure layer-a lithium-containing metal body-a lithium-embeddable current collecting structure layer, wherein the insulating sealing frame 201 is arranged on the peripheral edge of the sandwich composite structure 208, and the insulating sealing frame 201 is in a shape of a Chinese character 'hui', and is fixedly sealed with the peripheral edge of the sandwich composite structure. The negative electrode tab 2 further includes a negative electrode tab 203, and the negative electrode tab 203 may be electrically connected to the lithium embeddable current collecting structure layer 202, or may be electrically connected to both the lithium-containing metal body 205 and the lithium embeddable current collecting structure layer 202. A separation layer 4 through which lithium ions can pass but electrons cannot pass may be further provided on the outer side of the sandwich composite structure 208.
Fig. 3 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to a first embodiment of the present invention. In this embodiment, the lithium-embeddable current collecting structure layer 202 is a current collecting porous portion 204, and a lithium-containing metal body 205 is provided between the two current collecting porous portions 204. The current collecting porous portion 204 may be a porous lithium-intercalatable metal conductive layer or a porous conductive layer coated with a lithium-intercalatable material. Here, the current collecting porous portion 204 can function as a current collector while inserting lithium ions. The lithium-containing metal body 205 is fixed to the manifold porous portion 204 by welding, spraying, bonding, electrochemical plating, electroless plating, or mechanical press-fitting. When the lithium paste battery is overcharged or rapidly charged at a large rate, lithium ions will be intercalated into the porous lithium-intercalatable metal of the current-collecting porous portion 204 or the lithium-intercalatable material of the surface of the porous conductive layer. In this way, the lithium ion intercalation reaction occurring on the negative electrode does not become a deposition of lithium metal on the surface of the negative electrode, thus avoiding the formation of lithium dendrites on the surface of the negative electrode sheet.
Fig. 4 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to a second embodiment of the present invention. In this embodiment, the lithium-intercalatable current collecting structure layer 202 includes a current collecting porous portion 204 and a paste portion 206. Two lithium-embeddable current collecting structure layers 202 are provided on both sides of the lithium-containing metal body 205 in such a manner that the paste section 206 is adjacent to the lithium-containing metal body 205. The current collecting porous portion 204 may be a porous lithium-intercalatable metal conductive layer or a porous conductive layer coated with a lithium-intercalatable material. The paste portion 206 is a mixture of a lithium-intercalatable material, a conductive agent, and an electrolyte, wherein the volume content of the lithium-intercalatable material is 10% to 80%, and the volume content of the conductive agent is 0.1% to 5%. In this embodiment, both the manifold porous portion 204 and the paste portion 206 are capable of intercalating lithium ions during charging. It should be noted, however, that according to the present invention, only one of the manifold porous portion 204 and the paste portion 206 may be capable of intercalating lithium ions during charging.
When the lithium paste battery is overcharged or rapidly charged at a large rate, lithium ions will be intercalated into the porous lithium-intercalatable metal of the current-collecting porous portion 204 or the lithium-intercalatable material of the surface of the porous conductive layer. In this way, the lithium ion intercalation reaction occurring in the negative electrode does not become deposition of lithium metal on the surface of the negative electrode, and the growth of lithium dendrites can be inhibited by the rheological action of the slurry. Therefore, the formation of lithium dendrites on the surface of the negative electrode sheet is avoided.
In addition, when the paste portion 206 contains a lithium intercalatable material, the paste portion 206 also has a function of storing lithium during charging. Therefore, during the discharge of the battery, lithium ions can be extracted from the lithium-containing metal body 205 and also from the slurry portion 206, increasing the storage capacity of the battery.
Fig. 5 is a schematic cross-sectional view of a negative electrode sheet of a lithium paste battery according to a third embodiment of the present invention. In this embodiment, the manifold porous portion 204 has a multilayer structure, and the other structure of the negative electrode tab 2 is the same as that of the first embodiment shown in fig. 3 or the second embodiment shown in fig. 4. In this embodiment, the manifold porous portion 204 includes a plurality of porous layers 207, and the material, thickness, porosity, and pore size range of each porous layer 207 may be the same or different. For example, the current collecting porous portion 204 may include two porous layers 207, one being a porous lithium-intercalatable metal conductive layer, one being a porous conductive layer coated with a lithium-intercalatable material, or simply a porous conductive layer. The two porous layers 207 are joined together by means of gluing, welding or the like. The material, thickness, porosity and pore size range of each porous layer 207 may be adjusted according to actual needs.
Fig. 6 is a charge and discharge test chart of a battery with a negative plate of a lithium plate and a negative plate of a composite structure of an aluminum mesh and the lithium plate under different multiplying powers, wherein the positive electrode is a lithium iron phosphate coated plate, and the negative plate of fig. 6(a) is the lithium plate; the negative electrode sheets in fig. 6(b) and (c) have a composite structure of an aluminum mesh and a lithium sheet. As can be seen from the charge and discharge curves at different rates shown in fig. 6(a) and 6(b), the rate performance of the battery with the added lithium intercalation aluminum mesh is better, and the voltage plateau of lithium intercalation of the aluminum mesh can be seen from the battery charge curve of fig. 6 (c).
Fig. 7 is a test chart of a lithium intercalation slurry, and fig. 7(a) is a charge and discharge test of a graphite slurry half cell, and it can be seen that since a large amount of lithium needs to be consumed to form an SEI film, the graphite slurry has a first irreversible capacity ratio of approximately 50%, and if the partially consumed lithium is entirely supplied from a positive electrode, the reversible capacity of the cell is greatly reduced; fig. 7(b) is a battery charge and discharge test in which the positive electrode is a lithium iron phosphate pole piece and the negative electrode is graphite slurry, and it can be seen from the figure that the battery has a serious capacity fading after the first charge due to a considerable first irreversible lithium consumption; fig. 7(c) shows a battery charge and discharge test in which the positive electrode is a lithium iron phosphate pole piece, and the negative electrode is a lithium-containing sheet and graphite slurry.
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 (12)
1. A negative plate of a lithium slurry battery is characterized in that: the negative plate comprises an insulating sealing frame, a lithium-containing metal body and a lithium-embeddable current collecting structure layer, wherein the lithium-embeddable current collecting structure layer, the lithium-containing metal body and the other lithium-embeddable current collecting structure layer form a sandwich composite structure, the insulating sealing frame seals the peripheral edge of the sandwich composite structure, the material of the lithium-embeddable current collecting structure layer contains a lithium-embeddable material capable of embedding lithium in the charging and discharging processes of a lithium slurry battery, the material of the lithium-containing metal body is metal lithium or a lithium-rich alloy, the lithium-embeddable current collecting structure layer comprises a current collecting porous part and a slurry part, the slurry part is adjacent to the current collecting porous part, or the slurry in the slurry part is partially or completely infiltrated into pores of the current collecting porous part, the two lithium-embeddable current collecting structure layers are arranged on two sides of the lithium-containing metal body in a mode that the slurry part is adjacent to the lithium-containing metal, the current collecting porous portion and/or the paste portion contain a lithium-intercalatable material capable of intercalating lithium during charge and discharge of the lithium paste battery.
2. The negative electrode sheet for a lithium paste battery according to claim 1, wherein the current collecting porous part has a thickness of 0.01 to 2000 μm, a through-hole porosity of 30 to 98%, a pore diameter ranging from 10nm to 2mm, and the paste part has a thickness of 0 to 2 mm.
3. The negative electrode sheet for a lithium paste battery according to claim 1, wherein the paste portion comprises an electrolyte and lithium intercalatable conductive particles that are flowable in the electrolyte, wherein the lithium intercalatable conductive particles comprise 10 to 90% by mass of the paste portion and have an average particle diameter of 500nm to 500 μm,
the conductive lithium intercalatable particles are a compound or a mixture of a lithium intercalatable material and a conductive agent, wherein the mass ratio of the lithium intercalatable material to the conductive agent is 0-98: 100-2, the compounding or mixing mode comprises surface coating, bonding or mechanical mixing, and the conductive agent is one or more of graphene, carbon nanotubes, carbon fibers, amorphous carbon or metal conductive particles.
4. The negative electrode sheet for a lithium paste battery according to any one of claims 1 to 3, wherein the current collecting porous portion comprises a single porous layer; alternatively, the current collecting porous portion includes a plurality of porous layers, each of which is the same or different in material, thickness, porosity, and pore size, and the porous layers are connected together by welding, spraying, bonding, or mechanical pressing.
5. The negative electrode sheet of the lithium slurry battery according to any one of claims 1 to 3, wherein the insulating sealing frame is hermetically fixed at the peripheral edge of the sandwich composite structure by means of hot pressing or pasting, the material of the insulating sealing frame is 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 and sodium carboxymethylcellulose.
6. The negative electrode sheet of the lithium slurry battery according to any one of claims 1 to 3, wherein the surface of the negative electrode sheet is provided with an electronically insulating ionically conductive separator layer, and the material of the separator layer is an electronically nonconductive porous polymer material; or the isolating layer is made of a porous material compounded by an electronic non-conductive inorganic non-metallic material and an organic polymer; or the isolating layer is made of a gel polymer electrolyte composite material formed by compounding an electronic non-conductive polymer matrix, a liquid organic plasticizer and lithium salt; or the isolating layer is made of a porous polymer material with electronic non-conductivity or a porous material compounded by an inorganic non-metal material and an organic polymer, and the pores of the porous polymer material are impregnated with ion-conductive electrolyte or a polymer colloid material.
7. The negative electrode sheet for a lithium slurry battery according to claim 6, wherein the electronically non-conductive porous polymer material is polyethylene, polypropylene or polyvinylidene fluoride; the porous material compounded by the electronic non-conductive inorganic non-metallic material and the organic polymer is synthetic fiber non-woven fabric.
8. The negative electrode sheet for a lithium paste battery according to claim 1, wherein the lithium-containing metal body, the current collecting porous portion, and the paste portion are fixedly connected by the insulating sealing frame.
9. The negative electrode sheet of the lithium paste battery according to any one of claims 1 to 3, wherein the negative electrode sheet is provided with a negative electrode tab electrically connected to the current collecting porous portion of the lithium-embeddable current collecting structure layer or to the lithium-containing metal body; or, the negative electrode tab is electrically connected with the current collecting porous part of the lithium-embeddable current collecting structure layer and is electrically connected with the lithium-containing metal body.
10. The negative electrode sheet for a lithium paste battery according to claim 4, wherein at least one of the porous layers in the current collecting porous portion is a porous lithium-embeddable metal conductive layer, which is a metal mesh, and a mesh is a polygon; or, the porous lithium-embeddable metal conductive layer is a porous foam metal layer with a porous structure; or the porous lithium-embeddable metal conducting layer is formed by mechanically stamping or chemically corroding a metal plate or a metal foil;
and the material of the porous lithium embeddable metal conducting layer is aluminum, aluminum lithium alloy, tin-based alloy, lithium silicon alloy and lithium titanium alloy lithium embeddable metal, and the thickness is 0.5 mm-1 mm.
11. The negative electrode sheet for a lithium paste battery according to claim 4, wherein at least one of the porous layers in the current collecting porous portion is a porous conductive layer coated with a lithium intercalatable material,
the porous conducting layer is a conducting metal layer, the conducting metal layer is a metal net, 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; wherein the conductive metal layer is made of stainless steel, nickel, titanium, silver, tin-plated copper or nickel-plated copper; or
The porous conducting layer is carbon fiber conducting cloth, metal wire and organic fiber mixed conducting cloth; or
The porous conducting layer is a porous organic material with a surface coated with a conducting coating or plated with a metal film, and the porous organic material comprises natural cotton and linen, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene;
the lithium-embeddable material is one or more of aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metallic lithium powder and graphite which can embed lithium.
12. The negative electrode sheet for a lithium paste battery according to claim 4, wherein at least one of the porous layers in the current collecting porous portion is a porous mixture of a lithium intercalatable material, a conductive filler and a binder or a porous mixture of a lithium intercalatable material, a conductive filler and a polymer electrolyte, the mass fraction of the conductive filler is not less than 70%, the mass fraction of the lithium intercalatable material is not less than 10%, wherein,
the lithium-embeddable material is one or more of aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metal lithium powder and graphite which can embed lithium;
the conductive filler is one or more of carbon black, carbon nano tubes, carbon fibers, graphene, titanium powder, aluminum powder, silver powder, alloy aluminum powder, stainless steel powder, lithium-rich silicon powder, lithium-containing alloy powder metal alloy conductive particles and lithium-containing carbon materials;
the binder 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 and sodium carboxymethylcellulose;
the polymer electrolyte is a gel polymer electrolyte composite material formed by compounding a polymer matrix, a liquid organic plasticizer and lithium salt.
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| CN201610621508.2A CN107681115B (en) | 2016-08-01 | 2016-08-01 | Negative plate of lithium slurry battery |
| 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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| US11233276B2 (en) | 2017-04-07 | 2022-01-25 | Beijing Hawaga Power Storage Technology Company Ltd. | Lithium slurry battery system |
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