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CN112670450A - Negative pole piece for solid-state battery and preparation method and application thereof - Google Patents

Negative pole piece for solid-state battery and preparation method and application thereof Download PDF

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Publication number
CN112670450A
CN112670450A CN202011583537.7A CN202011583537A CN112670450A CN 112670450 A CN112670450 A CN 112670450A CN 202011583537 A CN202011583537 A CN 202011583537A CN 112670450 A CN112670450 A CN 112670450A
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lithium
lithium metal
solid
state battery
combination
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黄海强
陈少杰
王磊
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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    • H01M4/64—Carriers or collectors
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
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    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
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    • 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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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention provides a negative pole piece for a solid-state battery and a preparation method and application thereof. The negative pole piece comprises a copper foil, a lithium metal layer, a lithium nitride layer and an organic-inorganic composite layer which are sequentially stacked. According to the invention, ultrathin and uniform electroplated lithium metal is used as a base material, surface modification is carried out on the surface of the ultrathin and uniform electroplated lithium metal through nitrogen, so that the lithium metal is uniformly deposited, short circuit is prevented, the loss of a lithium source in the circulation process is reduced, the surface of the treated lithium metal is compounded through an organic-inorganic composite coating, so that the lithium metal deposited by charging is more uniformly and compactly deposited, the short circuit is effectively inhibited, the interface reaction generated by direct contact of the lithium metal and an electrolyte is inhibited, and the cycle is promoted, so that the technical problem that the lithium metal is difficult to apply in an all-solid-state battery is.

Description

Negative pole piece for solid-state battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid-state batteries, and relates to a negative pole piece for a solid-state battery, and a preparation method and application thereof.
Background
With the continuous improvement of the energy density requirement and the safety requirement of a battery module in the passenger electric vehicle market, the energy density of the traditional liquid ion battery can not meet the market requirement gradually, and meanwhile, the continuous occurrence of spontaneous combustion safety accidents also brings doubt to the electric trend of a passenger vehicle.
The solid-state battery is a main scheme for solving the energy density and safety defects of the traditional liquid battery, and attracts attention by the characteristics of mass energy density up to 400Wh/kg and no spontaneous combustion. At present, the research on solid-state batteries by various large companies and research institutions is far less deep than that of liquid-state batteries, the high energy density of the solid-state batteries is also established theoretically and computationally, and the realization of the design of the mass energy density of 400Wh/kg still has great difficulty. Lithium metal anodes must be used for anodes with a mass energy density of up to 400Wh/kg for design purposes, which is not achieved with conventional silicon, graphite and silicon carbon anodes. In practical application, the lithium metal negative electrode also has the problems of short-circuit failure of the battery, reaction passivation of a contact interface with an electrolyte and the like caused by the fact that the lithium metal negative electrode is pressed and expanded in the battery manufacturing and assembling process, pulverized in the circulating process, expanded in high volume, and long lithium dendrites pierce the electrolyte membrane, so that the lithium metal negative electrode can be applied to the all-solid-state battery only by special treatment.
CN107305950A discloses a polymer protective film, a metallic lithium negative plate and a lithium ion battery. The surface of the metallic lithium negative electrode sheet is coated with a polymer protective film containing polymer ionic liquid. However, due to the fluidity of the liquid, coating unevenness is easily caused, and the lithium metal secondary battery using the coating as the negative electrode causes current density unevenness during the cycle, and then lithium dendrites are generated, resulting in deterioration of the battery performance.
CN104617259A discloses a method for in-situ protection treatment of lithium negative electrode. The lithium metal treated by the lithium negative electrode in-situ protection can be used for high-performance lithium secondary batteries. The method for the in-situ protection treatment of the lithium negative electrode comprises a method for in-situ generation of silicon dioxide on the surface of the lithium negative electrode. At a certain temperature, the treatment liquid reacts with the passivation layer on the surface layer of the metal lithium to obtain the protective layer containing silicon dioxide. However, the formed protective film is brittle and fragile, and the problem of the lithium negative electrode cannot be solved.
The problems encountered in the application of the conventional lithium metal negative electrode in the all-solid-state battery, such as short-circuit failure of the battery caused by pressure extension in the battery manufacturing and assembling process, pulverization in the circulating process, high volume expansion, long lithium dendrite puncturing an electrolyte membrane and the like, reaction passivation on a contact interface with the electrolyte and the like, are to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a negative pole piece for a solid-state battery and a preparation method and application thereof. According to the invention, ultrathin and uniform electroplated lithium metal is used as a base material, surface modification is carried out on the surface of the ultrathin and uniform electroplated lithium metal through nitrogen, so that the lithium metal is uniformly deposited, short circuit is prevented, the loss of a lithium source in the circulation process is reduced, the surface of the treated lithium metal is compounded through an organic-inorganic composite coating, so that the lithium metal deposited by charging is more uniformly and compactly deposited, the short circuit is effectively inhibited, the interface reaction generated by direct contact of the lithium metal and an electrolyte is inhibited, and the cycle is promoted, so that the technical problem that the lithium metal is difficult to apply in an all-solid-state battery is.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a negative electrode plate for a solid-state battery, which comprises a copper foil, a lithium metal layer, a lithium nitride layer and an organic-inorganic composite layer which are sequentially stacked.
According to the negative pole piece provided by the invention, the lithium nitride layer on the surface of the lithium metal layer can ensure that lithium ions are uniformly deposited on the surface of the lithium metal to prevent dendritic crystal growth and passivate the surface of the lithium metal to slow the reaction speed of the lithium metal and electrolyte, and the organic-inorganic composite layer further inhibits the interface reaction generated by the contact of the lithium metal and the electrolyte and has the effect of inhibiting the volume expansion generated by lithium deposition and uneven porous fluffy accumulation of the lithium metal. The general organic polymer coating has low ionic conductivity and electronic conductivity at room temperature, and is not beneficial to rate performance at room temperature, and the organic-inorganic composite layer has the characteristics of high conductivity while having flexible elasticity, and is more beneficial to performance at room temperature.
Preferably, the thickness of the lithium metal layer is 1 to 10 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm.
In the invention, the volume energy density of the whole battery is influenced by the excessive thickness of the lithium metal layer, and short circuit caused by the denaturation and extension of the lithium metal is easy to occur in the subsequent battery manufacturing process.
Preferably, the thickness of the lithium nitride layer is 100nm to 1 μm, such as 100nm, 200nm, 400nm, 500nm, 800nm, or 1 μm.
In the present invention, the resistance increases due to the lithium nitride being too thick, and the lithium nitride being too thin does not prevent short-circuiting.
Preferably, the organic-inorganic composite layer has a thickness of 20 to 80 μm, for example, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, or 80 μm.
In the invention, the excessive thickness of the organic-inorganic composite layer can cause impedance increase to influence the rate capability of the battery, and the excessive thickness of the organic-inorganic composite layer cannot play a role in protecting an interface.
Preferably, the raw materials in the organic composite layer include a lithium salt, a polymer, and inorganic particles;
preferably, the lithium salt includes LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4Or LiBOB, or a combination of at least two of the same.
In the invention, the LiTFSI is lithium bis (trifluoromethane sulfonyl) imide, the LiFSI is lithium bis (fluorosulfonyl) imide, the LiDFOB is lithium difluoro oxalate borate, the LiPF6 is lithium hexafluorophosphate and LiBF4Is lithium tetrafluorophosphate, LiClO4Lithium perchlorate and LiBOB lithium bis (oxalato) borate.
Preferably, the polymer comprises any one of, or a combination of at least two of, PEO, PVDF-HFP, PPC, PAN, PEGDMA, PEGMEA, PMMA, or PEG.
In the invention, the PEO is polyethylene oxide, the PVDF-HFP is a polyvinylidene fluoride-hexafluoropropylene copolymer, the PPC is polymethyl ethylene carbonate, the PAN is polyacrylonitrile, the PEGDMA is polyethylene glycol dimethacrylate, the PEGMEA is propylene glycol monomethyl ether acetate, the PMMA is polymethyl methacrylate, and the PEG is polyethylene glycol.
Preferably, the inorganic particles comprise nano-LTO, nano-silicon, nano-LATP, LLZO, indium, aluminum, graphene, carbon nanotubes, carbon nanofibers, or the like.
In a second aspect, the present invention provides a method for preparing the negative electrode plate for the solid-state battery according to the first aspect, wherein the preparation method comprises the following steps:
(1) electroplating lithium metal on the copper foil to obtain a lithium-copper composite substrate, spraying nitrogen on the surface of the lithium metal in the lithium-copper composite substrate, and forming a lithium nitride layer on the surface of the lithium metal to obtain a surface-treated lithium-copper composite substrate;
(2) and (2) mixing lithium salt, polymer, inorganic particles and a solvent to obtain slurry, curing the slurry, and compounding the cured slurry with the surface-treated lithium-copper composite base material in the step (1) to obtain the negative pole piece.
According to the invention, a lithium metal layer is formed on the surface of the copper foil in an electroplating manner, the problem of extension of lithium metal in a battery assembling and pressurizing process can be solved by electroplating, the quality and energy density can be improved, and meanwhile, the lithium metal grown by electroplating is more uniform and compact than the surface of the lithium metal formed by rolling and has fewer heterogeneous defects; the lithium nitride layer is formed on the surface of the lithium metal in an in-situ growth mode in a spraying mode, so that the thickness of the lithium nitride is more uniform and controllable, and an organic-inorganic composite layer is compounded on the basis, so that the lithium metal deposited by charging deposition is more uniform and compact, the short circuit is effectively inhibited, the interface reaction generated by the direct contact of the lithium metal and an electrolyte is inhibited, the cycle performance of the battery is improved, and the technical problem that the lithium metal is difficult to apply in the all-solid-state battery is solved.
Preferably, the spraying method in the step (1) comprises spraying nitrogen gas on the surface of the lithium metal by using a continuous gas heating spraying device communicated with a nitrogen gas pipe.
Preferably, the mixing method of step (2) includes dissolving the polymer and the lithium salt into the solvent, and then adding the inorganic particles to obtain a slurry.
Preferably, after the curing operation in step (2), the cured material is dried.
Preferably, the compounding method of step (2) comprises transferring and/or plate hot pressing.
Preferably, the lithium salt of step (2) comprises LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4Or LiBOB, or a combination of at least two of the same.
Preferably, the polymer of step (2) comprises any one of PEO, PVDF-HFP, PPC, PAN, PEGDMA, PEGMEA, PMMA or PEG or a combination of at least two thereof.
Preferably, the inorganic particles of step (2) comprise nano LTO, nano silicon, nano LATP, LLZO, indium, aluminum, graphene, carbon nanotubes or carbon nanofibers, etc.
Preferably, the solvent comprises any one or a combination of at least two of hydrocarbons, nitriles, benzenes, ethers or ketones, preferably any one or a combination of at least two of acetonitrile, toluene, tetrahydrofuran, toluene, monochlorobenzene or methylformamide.
As a preferable technical scheme, the preparation method of the negative electrode plate for the solid-state battery comprises the following steps:
(1) electroplating lithium metal on the copper foil to obtain a lithium-copper composite base material, and then spraying nitrogen on the surface of the lithium metal in the lithium-copper composite base material by using continuous gas heating and spraying equipment communicated with a nitrogen pipe to form a lithium nitride layer on the surface of the lithium metal to obtain the surface-treated lithium-copper composite base material;
(2) dissolving a polymer and a lithium salt into a solvent, adding inorganic particles to obtain slurry, curing and drying the slurry, and compounding the dried slurry and the lithium-copper composite base material subjected to surface treatment in the step (1) in a flat plate hot pressing manner to obtain the negative pole piece;
wherein the lithium salt comprises LiTFSI, LiFSI, LiDFOB, LiPF6、LiBF4、LiClO4Or LiBOB, or a combination of at least two of the same;
the polymer comprises any one or a combination of at least two of PEO, PVDF-HFP, PPC, PAN, PEGDMA, PEGMEA, PMMA or PEG;
the inorganic particles comprise nano LTO, nano silicon, nano LATP, LLZO, indium, aluminum, graphene, carbon nano tubes or carbon nano fibers and the like;
the solvent comprises any one or the combination of at least two of hydrocarbons, nitriles, benzenes, ethers or ketones, preferably any one or the combination of at least two of acetonitrile, toluene, tetrahydrofuran, toluene, monochlorobenzene or methyl formamide.
In a third aspect, the present invention also provides a solid-state battery comprising a positive electrode, a sulfide electrolyte membrane, and a negative electrode obtained from the negative electrode sheet for a solid-state battery according to the first aspect.
Preferably, the positive electrode active material in the positive electrode includes any one of lithium cobaltate, NCM, or lithium iron phosphate, or a combination of at least two of them.
Preferably, the sulfide electrolyte membrane includes thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2Or Li2S-B2S3Any one or a combination of at least two of them.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the negative pole piece for the solid-state battery, the lithium nitride layer on the surface of the lithium metal layer can enable lithium ions to be uniformly deposited on the surface of the lithium metal, the surface of the lithium metal is passivated while dendritic crystal growth is prevented, the reaction speed of the lithium metal and an electrolyte is slowed, the organic-inorganic composite layer further inhibits the interface reaction generated by the contact of the lithium metal and the electrolyte and has the effect of inhibiting lithium deposition and volume expansion generated by uneven porous fluffy accumulation of the lithium metal, meanwhile, the organic-inorganic composite layer has the characteristics of high conductivity while having flexibility and elasticity, and is more beneficial to exerting the normal temperature performance, the cycle performance of the solid-state battery is improved, the capacity retention rate of the solid-state battery at 0.1C can reach 86.55% or more, the solid-state battery can still normally discharge at 0.3C, and the specific discharge capacity of the solid-state battery can reach 158 m.
(2) According to the invention, a lithium metal layer is formed on the surface of the copper foil in an electroplating manner, the problem of extension of lithium metal in a battery assembling and pressurizing process can be solved by electroplating, the quality and energy density can be improved, and meanwhile, the lithium metal grown by electroplating is more uniform and compact than the surface of the lithium metal formed by rolling and has fewer heterogeneous defects; the lithium nitride layer is formed on the surface of the lithium metal in an in-situ growth mode in a spraying mode, so that the thickness of the lithium nitride is more uniform and controllable, and on the basis, the organic-inorganic composite layer is compounded, so that the cycle performance of the battery is improved, and the technical problem that the lithium metal is difficult to apply in the solid-state battery is solved.
Drawings
Fig. 1 is a schematic structural diagram of a negative electrode tab provided in example 1.
Fig. 2 is a schematic structural diagram of a solid-state battery provided in embodiment 1.
Fig. 3 is a schematic view of the structure of the solid-state battery provided in comparative example 1.
Fig. 4 is a graph showing the performance of the solid-state battery provided in example 1.
Fig. 5 is a graph of performance of the symmetrical cell provided in example 1.
Fig. 6 is a graph showing the performance of the solid-state battery provided in comparative example 1.
Fig. 7 is a graph of the performance of the symmetrical cell provided in comparative example 1.
1-copper foil, 2-lithium metal layer, 3-lithium nitride layer, 4-organic-inorganic composite layer, 5-electrolyte membrane, 6-anode active material layer and 7-aluminum foil.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a negative electrode sheet for a solid-state battery, which comprises, as shown in fig. 1, a copper foil 1 having a thickness of 5 μm, a lithium metal layer 2 having a thickness of 5 μm, a lithium nitride layer 3 having a thickness of 0.5 μm, and an organic-inorganic composite layer 4 having a thickness of 50 μm, which are stacked in this order.
The preparation method of the negative pole piece comprises the following steps:
(1) electroplating 5 μm thick lithium metal on the surface of copper foil 1 as the base material of the lithium-copper composite tape, placing the lithium-copper composite tape on a planar vacuum panel, fixing, and spraying at 150 deg.C with 0.5Mpa and 0.03m/S to generate a layer of lithium nitride (Li) in situ3N) layer to obtain the surface-treated lithium-copper composite base material.
(2) 30 parts of PMMA polymer and 10 parts of LiTFSi are dissolved in anisole, 60 parts of 50-nanometer LATP particles are added, and the mixture is homogenized, coated on a substrate and dried. Coating the prepared organic-inorganic composite material on a substrate, placing the substrate under an ultraviolet curing instrument for curing, and then placing the substrate in a vacuum drying oven to remove the residual solvent. And (3) compounding the coated organic-inorganic composite layer with the lithium-copper composite base material subjected to surface treatment in the step (1) in a flat plate hot pressing mode to obtain the negative pole piece.
Example 1 provides a battery comprising a negative electrode including a copper foil 1, a lithium metal layer 2, a lithium nitride layer 3 and an organic-inorganic composite layer 4 sequentially stacked, an electrolyte membrane 5 and a positive electrode including a positive active material layer 6 and an aluminum foil 7, as shown in fig. 2, and a symmetric battery using the novel lithium metal material of example 1, as shown in fig. 4 and 5, at 0.5mAh/cm2The current density of the battery can be normally circulated, the current density of the full battery can be normally circulated at 0.3C, and the specific capacity can reach 190 mAh/g.
Example 2
The present embodiment provides a negative electrode plate for a solid-state battery, which includes a copper foil with a thickness of 5 μm, a lithium metal layer with a thickness of 1 μm, a lithium nitride layer with a thickness of 100nm, and an organic-inorganic composite layer with a thickness of 80 μm, which are sequentially stacked.
The preparation method of the negative pole piece comprises the following steps: (1) electroplating 5 μm thick lithium metal on the surface of copper foil 1Placing the lithium copper composite belt on a plane vacuum panel to fix the lithium copper composite belt as a base material of the lithium copper composite belt, and spraying a layer of lithium nitride (Li) on the surface of the lithium metal in situ at 150 ℃ by using continuous gas heating and spraying equipment communicated with a nitrogen pipe at the spraying pressure of 0.5Mpa and the spraying speed of 0.03m/S3N) layer to obtain the surface-treated lithium-copper composite base material.
(2) 30 parts of PMMA polymer and 10 parts of LiTFSi are dissolved in anisole, 60 parts of 50-nanometer LATP particles are added, and the mixture is homogenized, coated on a substrate and dried. Coating the prepared organic-inorganic composite material on a substrate, placing the substrate under an ultraviolet curing instrument for curing, and then placing the substrate in a vacuum drying oven to remove the residual solvent. And (3) compounding the coated organic-inorganic composite layer with the lithium-copper composite base material subjected to surface treatment in the step (1) in a flat plate hot pressing mode to obtain the negative pole piece.
Example 3
The present embodiment provides a negative electrode plate for a solid-state battery, which includes a copper foil 5 μm thick, a lithium metal layer 10 μm thick, a lithium nitride layer 1 μm thick, and an organic-inorganic composite layer 50 μm thick, which are sequentially stacked.
The preparation method of the negative pole piece comprises the following steps:
(1) electroplating 5 μm thick lithium metal on the surface of copper foil 1 as the base material of the lithium-copper composite belt, placing the lithium-copper composite belt on a plane vacuum panel, fixing, and spraying at 150 deg.C with a continuous gas heating spraying device communicated with a nitrogen pipe under 1Mpa and 0.01m/S to generate a layer of lithium nitride (Li) in situ3N) layer to obtain the surface-treated lithium-copper composite base material.
(2) 30 parts of PMMA polymer and 10 parts of LiTFSi are dissolved in anisole, 60 parts of 50-nanometer LATP particles are added, and the mixture is homogenized, coated on a substrate and dried. Coating the prepared organic-inorganic composite material on a substrate, placing the substrate under an ultraviolet curing instrument for curing, and then placing the substrate in a vacuum drying oven to remove the residual solvent. And (3) compounding the coated organic-inorganic composite layer with the lithium-copper composite base material subjected to surface treatment in the step (1) in a flat plate hot pressing mode to obtain the negative pole piece.
Example 4
The difference between this example and example 1 is that the thickness of lithium nitride in this example is 50 nm.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between this example and example 1 is that the thickness of lithium nitride in this example is 1.5 μm.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The present embodiment provides a negative electrode plate for a solid-state battery, where the negative electrode plate is a conventional 20 μm thick lithium-plated metal strip, a copper foil is 5 μm thick, and a lithium metal layer is 20 μm thick.
Comparative example 1 provides a solid-state battery comprising a negative electrode including a copper foil 1 and a lithium metal layer 2 sequentially stacked, an electrolyte membrane 5, and a positive electrode including a positive electrode active material layer 6 and an aluminum foil 7, as shown in fig. 3, while comparative example 1 provides a symmetrical battery at a large magnification of 0.5mAh/cm, as shown in fig. 6 and 72The charging and discharging conditions of (1) and the full cell was also short-circuited when charged at a current density of 0.3C.
Comparative example 2
The negative pole piece comprises a copper foil with the thickness of 5 mu m, a lithium metal layer with the thickness of 5 mu m and a lithium nitride layer with the thickness of 0.5 mu m which are sequentially stacked.
The preparation method of the negative pole piece comprises the following steps:
(1) electroplating 5 μm thick lithium metal on the surface of copper foil 1 as the base material of the lithium-copper composite tape, placing the lithium-copper composite tape on a planar vacuum panel, fixing, and spraying at 150 deg.C with 0.5Mpa and 0.03m/S to generate a layer of lithium nitride (Li) in situ3N) layer to obtain surface-treated lithium copperA composite substrate.
Comparative example 3
The present embodiment provides a negative electrode plate for a solid-state battery, which includes a copper foil with a thickness of 5 μm, a lithium metal layer with a thickness of 5 μm, and an organic-inorganic composite layer with a thickness of 50 μm, which are sequentially stacked.
The preparation method of the negative pole piece comprises the following steps:
(1) electroplating lithium metal with the thickness of 5 mu m on the surface of the copper foil 1 to be used as a lithium-copper composite tape base material, dissolving 30 parts of PMMA polymer and 10 parts of LiTFSi into anisole, adding 60 parts of 50-nanometer LATP particles, homogenizing, coating on the base material, and drying. Coating the prepared organic-inorganic composite material on a substrate, placing the substrate under an ultraviolet curing instrument for curing, and then placing the substrate in a vacuum drying oven to remove the residual solvent. And compounding the coated organic-inorganic composite layer with the lithium-copper composite substrate in a flat plate hot pressing mode to obtain the negative pole piece.
The negative electrode plate prepared in examples 1 to 5 and comparative examples 1 to 3, the positive electrode and the sulfide electrolyte membrane were assembled into a solid-state battery.
Wherein, the positive pole: the slurry contains NCM811 as a positive electrode active material and Li6PS5Cl, sulfide electrolyte is used as an ion conductor, conductive carbon and PVDF as a binder are added, the mass ratio of NCM811 to the sulfide electrolyte to the conductive carbon to the PVDF is 60:27:2:1, and a current collector is aluminum foil.
The assembly process is as follows: electrolyte LPS powder is used for dry pressing into sheets, and two sides of the sheets are assembled with the negative pole pieces provided by the examples 1-5 and the comparative examples 1-3 to form a symmetrical battery, and the performance of the symmetrical battery is tested in a mold; the integrated positive plate Li6PS5And (3) carrying out lamination assembly on an electrolyte membrane of Cl and the cathode pole pieces provided by the examples 1-5 and the comparative examples 1-3, wherein the structural schematic diagram of the solid-state battery obtained by assembling the example 1 is shown in figure 2, the structural schematic diagram of the solid-state battery obtained by assembling the comparative example 1 is shown in figure 3, and then the solid-state battery upper clamp prepared by the examples 1-5 and the comparative examples 1-3 is subjected to a 1-3MPa pressure test. The results are shown in table 1:
TABLE 1
Figure BDA0002865700920000111
Figure BDA0002865700920000121
From the data results of example 1 and examples 4 to 5, it is understood that when the lithium nitride layer in the negative electrode tab is too thin, short circuit due to growth of lithium dendrite is not prevented, and when it is too thick, the performance of the battery is degraded due to increase in polarization.
From the data results of example 1 and comparative example 1, it can be seen that the solid-state battery provided by the present invention has more excellent performance, specifically, the battery can be normally charged and discharged at a rate of 0.3C, and the battery performance has an obvious specific capacity advantage due to good interface protection.
From the data results of example 1 and comparative examples 2 to 3, it can be seen that the short circuit phenomenon occurs in the absence of the lithium nitride layer or the organic-inorganic composite layer in the negative electrode sheet.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The negative pole piece for the solid-state battery is characterized by comprising a copper foil, a lithium metal layer, a lithium nitride layer and an organic-inorganic composite layer which are sequentially stacked.
2. The negative electrode sheet for the solid-state battery according to claim 1, wherein the thickness of the lithium metal layer is 1 to 10 μm.
3. The negative electrode sheet for solid-state batteries according to claim 1 or 2, wherein the thickness of the lithium nitride layer is 100nm to 1 μm.
4. The negative electrode plate for the solid-state battery according to any one of claims 1 to 3, wherein the thickness of the organic-inorganic composite layer is 20 to 80 μm;
preferably, the raw materials in the organic composite layer include a lithium salt, a polymer, and inorganic particles;
the lithium salt includes LiTFSI, LiFSI, LiDFOB, LiPF6、LiBF4、LiClO4Or LiBOB, or a combination of at least two of the same;
preferably, the polymer comprises any one or a combination of at least two of PEO, PVDF-HFP, PPC, PAN, PEGDMA, PEGMEA, PMMA, or PEG;
preferably, the inorganic particles comprise nano-LTO, nano-silicon, nano-LATP, LLZO, indium, aluminum, graphene, carbon nanotubes, carbon nanofibers, or the like.
5. The preparation method of the negative electrode plate for the solid-state battery according to any one of claims 1 to 4, characterized by comprising the steps of:
(1) electroplating lithium metal on the copper foil to obtain a lithium-copper composite substrate, spraying nitrogen on the surface of the lithium metal in the lithium-copper composite substrate, and forming a lithium nitride layer on the surface of the lithium metal to obtain a surface-treated lithium-copper composite substrate;
(2) and (2) mixing lithium salt, polymer, inorganic particles and a solvent to obtain slurry, curing the slurry, and compounding the cured slurry with the surface-treated lithium-copper composite base material in the step (1) to obtain the negative pole piece.
6. The method for preparing the negative electrode sheet for the solid-state battery according to claim 5, wherein the spraying method in the step (1) comprises spraying nitrogen gas on the surface of the lithium metal by using a continuous gas heating spraying device communicated with a nitrogen gas pipe;
preferably, the mixing method of step (2) comprises dissolving the polymer and the lithium salt into the solvent, and then adding the inorganic particles to obtain a slurry;
preferably, after the curing operation in the step (2), drying the cured substance;
preferably, the compounding method of step (2) comprises transferring and/or plate hot pressing.
7. The method for preparing the negative electrode plate for the solid-state battery according to claim 5 or 6, wherein the lithium salt in the step (2) comprises LiTFSI, LiFSI, LiDFOB, LiPF6、LiBF4、LiClO4Or LiBOB, or a combination of at least two of the same;
preferably, the polymer of step (2) comprises any one of or a combination of at least two of PEO, PVDF-HFP, PPC, PAN, PEGDMA, PEGMEA, PMMA, or PEG;
preferably, the inorganic particles of step (2) comprise nano LTO, nano silicon, nano LATP, LLZO, indium, aluminum, graphene, carbon nanotubes or carbon nanofibers, etc.;
preferably, the solvent comprises any one or a combination of at least two of hydrocarbons, nitriles, benzenes, ethers or ketones, preferably any one or a combination of at least two of acetonitrile, toluene, tetrahydrofuran, toluene, monochlorobenzene or methylformamide.
8. The preparation method of the negative electrode plate for the solid-state battery according to any one of claims 5 to 7, characterized by comprising the steps of:
(1) electroplating lithium metal on the copper foil to obtain a lithium-copper composite base material, and then spraying nitrogen on the surface of the lithium metal in the lithium-copper composite base material by using continuous gas heating and spraying equipment communicated with a nitrogen pipe to form a lithium nitride layer on the surface of the lithium metal to obtain the surface-treated lithium-copper composite base material;
(2) dissolving a polymer and a lithium salt into a solvent, adding inorganic particles to obtain slurry, curing and drying the slurry, and compounding the dried slurry and the lithium-copper composite base material subjected to surface treatment in the step (1) in a flat plate hot pressing manner to obtain the negative pole piece;
wherein the lithium salt comprises LiTFSI, LiFSI, LiDFOB, LiPF6、LiBF4、LiClO4Or LiBOB, or a combination of at least two of the same;
the polymer comprises any one or a combination of at least two of PEO, PVDF-HFP, PPC, PAN, PEGDMA, PEGMEA, PMMA or PEG;
the inorganic particles comprise nano LTO, nano silicon, nano LATP, LLZO, indium, aluminum, graphene, carbon nano tubes or carbon nano fibers and the like;
the solvent comprises any one or the combination of at least two of hydrocarbons, nitriles, benzenes, ethers or ketones, preferably any one or the combination of at least two of acetonitrile, toluene, tetrahydrofuran, toluene, monochlorobenzene or methyl formamide.
9. A solid-state battery comprising a positive electrode, a sulfide electrolyte membrane, and a negative electrode obtained from the negative electrode sheet for a solid-state battery according to any one of claims 1 to 4.
10. The solid-state battery according to claim 9, wherein the positive electrode active material in the positive electrode includes any one of lithium cobaltate, NCM, or lithium iron phosphate, or a combination of at least two thereof;
preferably, the sulfide electrolyte membrane includes thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2Or Li2S-B2S3Any one or a combination of at least two of them.
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CN113140785A (en) * 2021-04-20 2021-07-20 惠州亿纬锂能股份有限公司 Modified solid electrolyte and preparation method and application thereof
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