CN113659192B - Sulfide all-solid-state battery cell, preparation method thereof and all-solid-state lithium ion battery - Google Patents

Sulfide all-solid-state battery cell, preparation method thereof and all-solid-state lithium ion battery Download PDF

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CN113659192B
CN113659192B CN202110977733.0A CN202110977733A CN113659192B CN 113659192 B CN113659192 B CN 113659192B CN 202110977733 A CN202110977733 A CN 202110977733A CN 113659192 B CN113659192 B CN 113659192B
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solid
sulfide
positive electrode
state
battery cell
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CN113659192A (en
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王磊
黄海强
李瑞杰
陈少杰
李生
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Svolt Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides an all-solid-state sulfide battery cell, a preparation method thereof and an all-solid-state lithium ion battery. The sulfide all-solid-state battery cell comprises all-solid-state unit battery cells and polymer films which are alternately stacked, wherein the all-solid-state unit battery cells and the polymer films are bonded through adhesive layers, and each all-solid-state unit battery cell comprises a first positive electrode, a first electrolyte layer, a double-sided negative electrode, a second electrolyte layer and a second positive electrode which are sequentially stacked. The polymer membrane can counteract at least partial shearing force in the all-solid-state unit cell, so that the shearing force born in the all-solid-state unit cell is relieved, the transmission of the shearing force to the inside of the all-solid-state unit cell and the adjacent all-solid-state unit cell is reduced, the interface impedance is reduced, the internal short circuit failure caused by high shearing force damage and current collector curling interference between the adjacent all-solid-state unit cells under the high pressure condition is prevented, and the consistency and the safety of the high-capacity sulfide all-solid-state unit cell are effectively improved by adjusting the number of the all-solid-state unit cells.

Description

Sulfide all-solid-state battery cell, preparation method thereof and all-solid-state lithium ion battery
Technical Field
The invention relates to the technical field of all-solid-state batteries, in particular to an all-solid-state sulfide battery cell, a preparation method thereof and an all-solid-state lithium ion battery.
Background
The solid-state battery adopts the nonflammable solid electrolyte to replace the flammable organic liquid electrolyte, so that the safety of the battery system is greatly improved, and the synchronous improvement of the energy density is realized. Among various new battery systems, solid-state batteries are the next generation technology closest to industrialization, which has become a consensus of industry and scientific community. Among them, sulfide electrolytes have relatively high lithium ion conductivity. The sulfide electrolyte mainly comprises thio-LISICON and Li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 、Li 2 S-B 2 S 3 And the ion conductivity at room temperature can reach 10 -3 ～10 -2 S/cm, is close to or even exceeds that of the organic electrolyte, and has high thermal stability, good safety performance and wide electrochemical stability window (more than 5V)Is characterized by outstanding advantages in high power and high-low temperature solid state batteries.
However, when the sulfide solid electrolyte is adopted to prepare the all-solid-state battery cell system, because the sulfide electrolyte belongs to ceramic materials, the adhesion force between particles is poor, the shape is irregular, and a tough and low-porosity independent electrolyte membrane is not easy to prepare, in order to ensure that the prepared electrolyte membrane has higher conductivity, the lower the content of the used binder is, the better the content is, the difficulty of preparing the electrolyte membrane with high conductivity and good mechanical strength is increased, the sulfide electrolyte is extremely unstable to moisture, and only the components (anode, cathode or electrolyte membrane) of the sulfide electrolyte are required to be manufactured in an inert gas environment in a glove box, the requirements on equipment and the electrolyte are extremely high, so that the difficulty and the cost of preparing the high-capacity all-solid-state battery cell (multi-layer stack) in a batch mode are increased, the manufacturing efficiency is reduced, and the cost of the manufacturing process is increased, and finally, the difficulty of preparing the high-performance sulfide solid-state battery cell is greatly increased. In order to ensure full solid-state battery capacity, reduce solid-state contact resistance, reduce the influence of volume expansion on solid-state contact in the whole charge and discharge process, and generally require high external pressure of about 1-10 MPa to maintain pressure in the full solid-state battery test or use process, and sometimes even pressure of more than 10 MPa. However, for all-solid-state battery structures, particularly for multi-layered laminated all-solid-state battery structures, high pressure may cause high shear forces between internal large and small components of the battery, and particularly for batteries with more laminated structures, the risk of internal short circuits is increased due to high shear forces, so that there is a need for a method for manufacturing sulfide all-solid-state battery cells capable of resisting internal high shear forces even under external high pressure conditions under the current materials and technical conditions.
Disclosure of Invention
The invention mainly aims to provide a sulfide all-solid-state battery cell, a preparation method thereof and an all-solid-state lithium ion battery, so as to solve the problem that the sulfide all-solid-state battery cell in the prior art is poor in internal high shear resistance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a sulfide all-solid-state battery cell including an all-solid-state unit battery cell and a polymer membrane alternately stacked, bonded by a glue layer, wherein the all-solid-state unit battery cell includes a first positive electrode, a first electrolyte layer, a double-sided negative electrode, a second electrolyte layer, and a second positive electrode stacked in this order.
Further, the distance between the projection edge of the double-sided negative electrode on the polymer membrane and the edge of the polymer membrane is less than or equal to 1mm, and the projection area of the double-sided negative electrode on the polymer membrane is less than or equal to the edge of the polymer membrane.
Further, the thermal expansion coefficient of the polymer film is 2×10 -5 ～3×10 -6 Between/deg.c, the young's modulus of the polymer film is preferably not less than 1Gpa, preferably the polymer film is selected from any one or more of PC film, PET film, PMMA film, PI film, PP film, preferably the thickness of the polymer film is between 10 μm and 1mm, preferably 30 to 100 μm.
Further, the glue layer is selected from one or more of PVDF-HFP glue layer, PVDFLBG glue layer, PVDF glue layer, SBR glue layer, SBS glue layer, SEBS glue layer, NBR glue layer and HNBR glue layer, and the thickness of the glue layer is preferably 0.5-1 μm independently.
Further, the first positive electrode includes a stacked first positive electrode current collector and a first positive electrode active layer, and the first positive electrode active layer is disposed in contact with the first electrolyte layer; the second positive electrode comprises a second positive electrode current collector and a second positive electrode active layer which are stacked, the second positive electrode active layer is contacted with a second electrolyte layer, preferably the first positive electrode active layer and the second positive electrode active layer respectively independently comprise a positive electrode active substance, and the positive electrode active substance has a chemical formula of LiNi x Co y M z O 2 Wherein x is greater than or equal to 0, y is greater than or equal to 0, z is greater than or equal to 0, and x+y+z=1, wherein M is selected from one or more of Mn, al, zr, ti, V, mg, fe, mo, preferably the positive electrode active material is coated withA coating layer, the coating layer being an ion conductor material, preferably selected from Li 2 TiO 3 、LiNbO 3 、Li 3 BO 3 、Li 2 ZrO 3 、LiCoO 3 、LiPO 3 、Li 2 MnO 4 、Al(PO 3 ) 3 、La(PO 3 ) 3 、NaPO 3 More preferably, the thickness of the coating layer is 1 to 10nm.
Further, the above-mentioned double-sided anode includes an anode current collector and anode active layers provided on opposite surfaces of the anode current collector, one anode active layer is provided in contact with the first electrolyte layer, the other anode active layer is provided in contact with the second electrolyte layer, preferably the two anode active layers each independently include an anode material selected from any one of Si alloy anode active material and carbon material, preferably the Si alloy anode active material includes any one or more of Fe, co, sb, bi, pb, ni, cu, zn, ge, in, sn or Ti and any one or more of solid solution obtained by silicon, silicon oxide, silicon carbide, silicon nitride; preferably the carbon material is selected from any one or more of hard carbon, soft carbon and graphite.
Further, the areas of the first positive electrode and the second positive electrode are respectively and independently smaller than the area of the double-sided negative electrode, the areas of the first electrolyte layer and the second electrolyte layer are respectively and independently larger than the area of the first positive electrode or the area of the second positive electrode, and the areas of the first electrolyte layer and the second electrolyte layer are respectively and independently smaller than or equal to the area of the double-sided negative electrode.
According to another aspect of the present invention, there is provided a method for preparing the sulfide all-solid state battery cell, including: and carrying out isostatic pressing compounding on the all-solid-state unit cell and the polymer membrane to obtain the sulfide all-solid-state cell.
Further, the isostatic pressing compounding is carried out at the temperature of 40-120 ℃, the pressure of 10-100 MPa, the dwell time of 1-60 min and the pressing times of 1-5 times.
According to still another aspect of the present invention, there is provided an all-solid-state lithium ion battery, including a battery cell, the battery cell being the sulfide all-solid-state battery cell described above.
By means of the technical scheme, the sulfide all-solid-state battery cell comprises the polymer membrane overlapped with the all-solid-state unit battery cell, at least partial shearing force in the all-solid-state unit battery cell can be counteracted by the polymer membrane, the shearing force born by the inside of the all-solid-state unit battery cell is relieved, the transmission of the shearing force to the inside of the all-solid-state unit battery cell and the adjacent all-solid-state unit battery cell is reduced, interface impedance is reduced, and internal short circuit failure caused by high shearing force damage and current collector curling interference between the adjacent all-solid-state unit battery cells under high pressure is prevented. Further, the capacity of the sulfide all-solid-state battery cell can be realized by adjusting the quantity of all-solid-state unit battery cells, and the consistency and the safety of the high-capacity sulfide all-solid-state battery cell are effectively improved.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed by the background technology, the sulfide all-solid-state battery cell in the prior art has the problem of poor internal high shear resistance, and in order to solve the problem, the invention provides the sulfide all-solid-state battery cell, a preparation method thereof and an all-solid-state lithium ion battery.
In one exemplary embodiment of the present application, a sulfide all-solid state battery cell is provided, which includes an all-solid state unit battery cell and a polymer membrane which are alternately stacked, and the all-solid state unit battery cell and the polymer membrane are bonded through a glue layer, wherein the all-solid state unit battery cell includes a first positive electrode, a first electrolyte layer, a double-sided negative electrode, a second electrolyte layer and a second positive electrode which are sequentially stacked.
Because the sulfide all-solid-state battery cell comprises the polymer membrane overlapped with the all-solid-state unit battery cell, the polymer membrane can offset at least partial shearing force in the all-solid-state unit battery cell, and the shearing force born by the inside of the all-solid-state unit battery cell is relieved, so that the transmission of the shearing force to the inside of the all-solid-state unit battery cell and the adjacent all-solid-state unit battery cell is reduced, the interface impedance is reduced, and the internal short circuit failure caused by the high shearing force damage and the current collector curling interference between the adjacent all-solid-state unit battery cells under the high pressure condition is prevented. Further, the capacity of the sulfide all-solid-state battery cell can be realized by adjusting the quantity of all-solid-state unit battery cells, and the consistency and the safety of the high-capacity sulfide all-solid-state battery cell are effectively improved.
In order to sufficiently alleviate the shearing force applied to each part of the double-sided negative electrode by the polymer film, it is preferable that the distance between the projected edge of the double-sided negative electrode on the polymer film and the edge of the polymer film is 1mm or less, and the projected area of the double-sided negative electrode on the polymer film is smaller than or equal to the edge of the polymer film.
In one embodiment of the present application, since the battery is in an exothermic state during operation, the thermal expansion coefficient of the polymer membrane is preferably 2×10 in order to avoid the decrease of the adhesion between the polymer membrane and the all-solid-state cell caused by the expansion and contraction of the polymer membrane due to the change of heat over a long period -5 ～3×10 -6 Between/deg.c, a polymer membrane having a coefficient of thermal expansion within the above-described range is advantageous for maintaining its shape in the operating state of the sulfide all-solid state cell. The polymer membrane preferably has a Young's modulus of not less than 1Gpa and a good strength within the above-mentioned required range, thereby contributing to the exertion of the damping effect thereof on the shearing force born by the inside of the all-solid-state unit cell. Preferably, the polymer membrane is selected from one or more of PC membrane, PET membrane, PMMA membrane, PI membrane and PP membrane, and the material of the polymer membrane can improve the strength and hardness of the polymer membrane and has the characteristic of light weight, so that the weight of the sulfide all-solid-state battery cell is not seriously loaded. The thickness of the polymer film is preferably between 10 μm and 1mm, preferably between 30 and 100 μm.
When the thickness of the polymer membrane is within the range, the polymer membrane can not only effectively play a role in relieving the shearing force born by the inside of the all-solid-state unit cell, but also prevent the sulfide all-solid-state cell from being too thick, so that the volume of the battery is too large.
In order to improve the fusion of the adhesive layer on the polymer membrane and the adhesive in the first positive electrode or the second positive electrode of the all-solid-state unit cell, so that the polymer membrane and the all-solid-state unit cell are combined more firmly, the adhesive layer is preferably selected from one or more of PVDF-HFP adhesive layer, PVDFLBG adhesive layer, PVDF adhesive layer, SBR adhesive layer, SBS adhesive layer, SEBS adhesive layer, NBR adhesive layer and HNBR adhesive layer. The polymer membrane is light in weight, and the thickness of the adhesive layers is preferably 0.5-1 mu m independently, so that the shearing force born by the inside of the all-solid-state unit cell can be effectively relieved, and the quality and the energy density of the all-solid-state cell are not greatly influenced. In addition, in the specific implementation process, the glue layer thickness is ensured to be uniform as much as possible, the electric performance is prevented from being influenced due to uneven internal pressure of the all-solid-state battery cell caused by inconsistent local thickness, and the electric performance of the all-solid-state battery cell is prevented from being influenced by residual solvent due to the fact that the all-solid-state battery cell is fully dried as much as possible.
In one embodiment of the present application, the first positive electrode includes a stacked first positive electrode current collector and a first positive electrode active layer, where the first positive electrode active layer is disposed in contact with the first electrolyte layer; the second positive electrode comprises a second positive electrode current collector and a second positive electrode active layer which are stacked, the second positive electrode active layer is contacted with a second electrolyte layer, preferably the first positive electrode active layer and the second positive electrode active layer respectively independently comprise a positive electrode active substance, and the positive electrode active substance has a chemical formula of LiNi x Co y M z O 2 Wherein x is greater than or equal to 0, y is greater than or equal to 0, z is greater than or equal to 0, and x+y+z=1, wherein M is selected from one or more of Mn, al, zr, ti, V, mg, fe, mo, preferably a coating layer is arranged outside the positive electrode active substance, the coating layer is an ion conductor material, preferably the ion conductor material is selected from Li 2 TiO 3 、LiNbO 3 、Li 3 BO 3 、Li 2 ZrO 3 、LiCoO 3 、LiPO 3 、Li 2 MnO 4 、Al(PO 3 ) 3 、La(PO 3 ) 3 、NaPO 3 More preferably, the thickness of the coating layer is 1 to 10nm.
The positive electrode active material with the ion conductor material coating layer has better conductivity, so that the first positive electrode and the second positive electrode of the type can be better matched with the double-sided negative electrode in a synergistic way, and the electrical property of the sulfide all-solid-state battery core is improved.
Preferably, each of the first positive electrode active layer and the second positive electrode active layer further comprises a conductive agent, a binder, and a sulfide solid electrolyte. Further, the preferred conductive agent is selected from any one or more of a zero-dimensional conductive agent, a one-dimensional conductive agent and a two-dimensional conductive agent, preferably the zero-dimensional conductive agent is an SP conductive agent and/or an AB conductive agent, preferably the one-dimensional conductive agent comprises a CNT conductive agent and/or a VGC conductive agent, preferably the two-dimensional conductive agent is graphene to enhance the conductivity of the first positive electrode and the second positive electrode as much as possible. The binder is preferably selected from any one or more of PVDF5130, PVDF75130, PVDF21216, PVD, F6020, PVDF-HVS900, PVDF-HFP and PVDF-LBG, NBR, HNBR, SBR, SBS, SEBS, PTEF, so as to improve the bonding strength of the multi-element positive electrode material, the conductive agent and the like with the first positive electrode current collector and the second positive electrode current collector as much as possible. Preferably the sulfide electrolyte is selected from the group consisting of thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 、LiI-LiBr-Li 2 S-P 2 S 5 And Li (lithium) 2 S-B 2 S 3 Any one or more of the following. The sulfide solid electrolyte has the characteristics of higher lithium ion conductivity, high thermal stability, good safety performance and wide electrochemical stability window (more than 5V), thereby being more beneficial to improving the performance of the sulfide all-solid-state battery core.
In one embodiment of the present application, the above-mentioned double-sided anode includes an anode current collector and anode active layers disposed on opposite surfaces of the anode current collector, one anode active layer is disposed in contact with the first electrolyte layer, the other anode active layer is disposed in contact with the second electrolyte layer, preferably the two anode active layers each independently include an anode material selected from any one of Si alloy anode active material and carbon material.
In order to further improve the electrical properties of the anode, it is preferable that the first anode active layer and the second anode active layer each independently include a solid electrolyte, a conductive agent, and a binder, and that the solid electrolyte is a sulfide electrolyte. The method is favorable for improving the cooperative coordination among the components, thereby ensuring the conductivity of the double-sided negative electrode and the cohesiveness between the components and the double-sided negative electrode current collector. Further, it is preferable that the sulfide electrolyte is selected from the group consisting of thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 、LiI-LiBr-Li 2 S-P 2 S 5 And Li (lithium) 2 S-B 2 S 3 Any one or more of the above is beneficial to improving the thermal stability, the safety performance and the energy density of the double-sided negative electrode. Preferably, the conductive agent is selected from one or more of a zero-dimensional conductive agent, a one-dimensional conductive agent and a two-dimensional conductive agent, preferably the zero-dimensional conductive agent is an SP conductive agent and/or an AB conductive agent, preferably the one-dimensional conductive agent comprises a CNT conductive agent and/or a VGC conductive agent, preferably the two-dimensional conductive agent is graphene, and the conductivity of the double-sided negative electrode is improved. Preferably, the binder is selected from any one or more of PAA, li-PAA, SBR, NBR, HNBR, SBR, SBS, SEBS, PTEF and PEO, which is advantageous for binding the components of the solid electrolyte, the conductive agent, etc. to the negative electrode current collector.
The structure of the double-sided negative electrode determines that the all-solid-state unit cell has two positive electrode structures, so that the use of a negative electrode current collector is saved, and the all-solid-state unit cell with simpler structure and better performance is obtained. The first electrolyte layer and the second electrolyte layer also independently comprise a binder and a sulfide solid electrolyte, and the thicknesses of the first electrolyte layer and the second electrolyte layer are preferably 10-50 μm independently. Preferably, the binder is selected from one or more of PVDF5130, PVDF75130, PVDF21216, PVD, F6020, PVDF-HVS900, PVDF-HFP, PVDF-LBG, NBR, HNBRSBR, SBS, SEBS, PTEF, thereby helping to improve the first electrolyte layer, the second electrolyte layer and the double-sided negative electrode and the first positive electrode respectivelyAnd the binding force of the second positive electrode. In addition, the thicknesses of the first electrolyte layer and the second electrolyte layer are preferably 10 to 50 μm independently, which is advantageous in reducing the transmission distance of lithium ions as much as possible and reducing the risk of polarization due to the too thick thickness of the first electrolyte layer and the second electrolyte layer. Preferably the sulfide solid electrolyte is selected from the group consisting of thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 、LiI-LiBr-Li 2 S-P 2 S 5 And Li (lithium) 2 S-B 2 S 3 Any one or more of the following. The sulfide solid electrolyte has the characteristics of higher lithium ion conductivity, high thermal stability, good safety performance and wide electrochemical stability window (more than 5V), thereby being more beneficial to improving the performance of the sulfide all-solid-state battery core.
To increase the energy density of the anode material, it is preferable that the Si alloy anode active material includes any one or more of a solid solution of any one or more of Fe, co, sb, bi, pb, ni, cu, zn, ge, in, sn or Ti and silicon, silicon oxide, silicon carbide, silicon nitride; preferably the carbon material is selected from any one or more of hard carbon, soft carbon and graphite.
Preferably, the areas of the first positive electrode and the second positive electrode are respectively and independently smaller than the area of the double-sided negative electrode, the areas of the first electrolyte layer and the second electrolyte layer are respectively and independently larger than the area of the first positive electrode or the area of the second positive electrode, the areas of the first electrolyte layer and the second electrolyte layer are respectively and independently smaller than or equal to the area of the double-sided negative electrode, and further, the edges of the double-sided negative electrode are preferably wider than the edges of the first positive electrode or the second positive electrode by 1-2 mm, so that the problem of edge short circuit is prevented.
In another exemplary embodiment of the present application, there is provided a method for preparing the sulfide all-solid state battery cell, including: and carrying out isostatic pressing compounding on the all-solid-state unit cell and the polymer membrane to obtain the sulfide all-solid-state cell.
The polymer membrane in the sulfide all-solid-state battery cell obtained by the preparation method can offset at least partial shearing force in the all-solid-state unit battery cell, and relieve the shearing force born by the inside of the all-solid-state unit battery cell, so that the transmission of the shearing force to the inside of the all-solid-state unit battery cell and the adjacent all-solid-state unit battery cell is reduced, the interface impedance is reduced, and further the internal short circuit failure caused by the high shearing force damage between the adjacent all-solid-state unit battery cells and the curling interference of the current collector under the high pressure condition is prevented. Furthermore, the isostatic pressing compounding can further compact the all-solid-state unit cells, interface impedance is reduced, and the adhesive in the positive poles of two adjacent all-solid-state unit cells and the adhesive layer on the polymer membrane are fused and fixed, so that the all-solid-state unit cells are integrated, and all layers are in flat and tight contact, so that the structural stability and performance exertion of the sulfide all-solid-state unit cells in the circulating process are facilitated.
The isostatic pressing compounding is carried out at the temperature of 40-120 ℃, the pressure of 10-100 MPa, the dwell time of 1-60 min and the pressing times of 1-5 times.
The isostatic pressing composite temperature and pressure are favorable for controlling the combination degree between the all-solid-state unit cell and the polymer membrane, and the temperature and pressure are favorable for fusion permeation between the composite layers when the temperature and the pressure are higher, so that the combination between the composite layers is firmer. The control of dwell time and number of presses is beneficial to control the compaction density of the all-solid-state cell. The isostatic pressing compounding is performed at the temperature of 40-120 ℃ to be more beneficial to promoting the melting of the carbon coating layer on the positive electrode of the all-solid-state unit cell, so that the carbon coating layer is better melted, bonded and fixed with the adhesive layer on the polymer membrane, and the plurality of all-solid-state unit cells are integrated, so that the structural stability and performance exertion of the obtained sulfide all-solid-state cell in the circulation process are facilitated.
In yet another exemplary embodiment of the present application, an all-solid-state lithium ion battery is provided that includes a cell that is a sulfide all-solid-state cell as described above.
The polymer membrane in the sulfide all-solid-state cell can offset at least partial shearing force inside the all-solid-state cell, and the shearing force born inside the all-solid-state cell is relieved, so that the shearing force is reduced to be transmitted to the inside of the all-solid-state cell and the adjacent all-solid-state cell, the interface impedance is reduced, and further the internal short circuit failure caused by high shearing force damage and current collector curling interference between the adjacent all-solid-state cell under the high pressure condition is prevented. Therefore, the all-solid-state lithium ion battery comprising the sulfide all-solid-state battery core has higher safety.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
The method is adopted to prepare the all-solid-state unit cell:
taking NCM811@LiNbO 3 As active material, LPSCl as electrolyte, SP and VGCF as conductive agent, PVDF-HFP as binder, NCM811, li 6 PS 5 Cl, (SP and VGCF) and PVDF-HFP are mixed according to the mass ratio of 65:30.5:1.5:3, then trimethylbenzene is used for dissolving PVDF-HFP to prepare glue solution, the materials are subjected to ball milling homogenization (the solid content of the slurry is 66 wt%) and are respectively coated on a carbon-coated aluminum foil for drying, and a first positive electrode and a second positive electrode are obtained after hot rolling at 75 ℃ for standby.
Mixing cyclohexanone and PVDF-HFP to prepare a glue solution; ball milling, mixing and pulping the mixed glue solution and LPSCl according to the mass ratio of 2:3 to obtain mixed slurry, respectively coating the slurry on the surface of PET, and drying to obtain a first electrolyte layer precursor and a second electrolyte layer precursor with film thickness of 20 mu m for later use.
Taking nano silicon, graphite and Li 6 PS 5 Cl, CNT, HNBR nanometer silicon, (graphite and CNT), li 6 PS 5 And (3) dissolving HNBR by using trimethylbenzene, stirring and mixing the glue solution and other components for homogenating (the solid content of the slurry is 55 wt%) and then respectively coating the glue solution and the other components on two sides of the carbon-coated copper foil, and then drying and hot rolling at 80 ℃ to obtain the double-sided battery cathode for later use.
Taking NCM811@LiNbO 3 As active substances, LPSCl as electrolyte, SP and VGCF as conductive agents, PVDF-HFP as binder, and trimethylbenzene to dissolve PVDF-HFP to prepare glue solution, ball milling and homogenizing the above materials, and respectively coatingAnd (3) drying the carbon-coated aluminum foil, and hot rolling at 75 ℃ to obtain a first positive electrode and a second positive electrode for standby.
Mixing cyclohexanone and PVDF-HFP to prepare a glue solution; ball milling, mixing and pulping the mixed glue solution and the LPSCl according to a proportion to obtain mixed slurry, respectively coating the slurry on the surface of PET, and drying to obtain a first electrolyte layer precursor and a second electrolyte layer precursor with film thickness of 20 mu m for later use.
And (3) dissolving HNBR (HNBR) by using trimethylbenzene, uniformly mixing the glue solution and other component materials, respectively coating the glue solution and other component materials on two sides of the carbon-coated copper foil, drying, and hot rolling at 80 ℃ to obtain the double-sided battery cathode for later use.
And respectively attaching the prepared first electrolyte layer precursor and the prepared second electrolyte layer precursor to two sides of the prepared double-sided negative electrode, vacuum packaging, then carrying out heat isostatic pressing and compounding at 450MPa and 90 ℃ for 20min, removing PET (polyethylene terephthalate) base materials on the surfaces of the first electrolyte layer precursor and the second electrolyte layer precursor, and obtaining the first electrolyte layer and the second electrolyte layer, wherein the cutting area is 4 x 4.5 cm.
And then respectively cutting the first positive electrode and the second positive electrode to 3.8 x 4.3cm, respectively attaching the first positive electrode and the second positive electrode to the first electrolyte layer and the second electrolyte layer, vacuum packaging, and then carrying out pressure maintaining for 30min and temperature isostatic pressing for 2 times at 500MPa and 85 ℃ to obtain the all-solid-state unit cell.
Example 1
Taking a 100 μm thick PI (polyimide) film (DuPont China group Co., ltd.) and using the same PVDF-HFP glue solution when preparing the positive electrode, coating a 0.5 μm PVDF-HFP glue layer on the PI film, and drying to obtain a PI film for later use.
Inserting 4 x 4.5cm PI film with thickness of 100 μm into the middle of 2 above all solid state unit cells, stacking, packaging, holding at 50MPa.90deg.C for 10min, isostatic pressing, unpacking, welding tab, and packaging to obtain sulfide all solid state cell.
Example 2
Example 2 differs from example 1 in that,
taking a PET film (DuPont China group Co., ltd.) with a thickness of 100 μm, using the same PVDF-HFP glue solution when preparing the positive electrode, coating a PVDF-HFP glue layer with a thickness of 0.5 μm on the PET film, and drying to obtain the PET film for later use.
And inserting the treated PET film sheets with the size of 4 x 4.5cm and the thickness of 100 mu m into the middle of the 2 all-solid-state unit cells, stacking and packaging, maintaining the temperature at 50MPa and 90 ℃ for 10min, pressing for one time by isostatic pressing, then unpacking, welding and packaging the electrode lugs, and finishing assembly to obtain the sulfide all-solid-state cell.
Example 3
Example 3 differs from example 1 in that,
taking a PMMA film (DuPont China group Co., ltd.) with a thickness of 100 μm, coating a PVDF-HFP glue layer with a thickness of 0.5 μm on the PMMA film by using the same PVDF-HFP glue solution when preparing the positive electrode, and drying to obtain the PMMA film for later use.
Inserting the treated PMMA films with the size of 4 x 4.5cm and the thickness of 100 mu m into the middle of 2 all-solid-state unit cells, stacking and packaging, maintaining the temperature at 50MPa and 90 ℃ for 5min, pressing for one time by isostatic pressing, then unpacking, welding and packaging the lugs, and finishing assembly to obtain the sulfide all-solid-state cell.
Example 4
Example 4 differs from example 1 in that,
the thickness of the PI film is 30 mu m, 2 all-solid-state unit cells are inserted into the PI film which is processed and has the size of 4 x 4.5cm and the thickness of 50 mu m to be overlapped and stacked and packaged, and (3) maintaining the pressure at 50MPa and 90 ℃ for 10min, carrying out isostatic pressing for one time, then unsealing, welding the tab, and packaging to complete assembly, thereby obtaining the sulfide all-solid-state battery cell.
Example 5
Example 5 differs from example 1 in that,
and inserting the PI film processed with the size of 4 x 4.5cm and the thickness of 120 μm into the middle of 2 all-solid-state unit cells, stacking and packaging the PI film, wherein the PI film is 80 μm thick, maintaining the pressure at 50MPa and 90 ℃ for 10min, pressing the PI film for one time under isostatic pressure, then unpacking, welding and packaging the electrode lugs, and finishing assembly to obtain the sulfide all-solid-state cell.
Example 6
Example 6 differs from example 1 in that,
and inserting the PI film processed with the size of 4 x 4.5cm and the thickness of 10 μm into the middle of 2 all-solid-state unit cells, stacking and packaging the PI film, wherein the PI film is 10MPa, 90 ℃ and the pressure is maintained for 10min, carrying out isostatic pressing for one time, then unpacking, welding and packaging the electrode lugs, and completing assembly to obtain the sulfide all-solid-state cell.
Example 7
Example 7 differs from example 1 in that,
and inserting the processed PI films with the thickness of 1mm and the size of 4 x 4.5cm into the middle of 2 all-solid-state unit cells, stacking and packaging the processed PI films, wherein the thickness of the processed PI films is 1mm, maintaining the pressure at 50MPa and 90 ℃ for 10min, pressing the PI films for one time under isostatic pressure, and then unpacking, welding and packaging the electrode lugs to finish the assembly to obtain the sulfide all-solid-state cell.
Example 8
Example 8 differs from example 1 in that,
and taking a 100-mu m thick PI film, using the same PVDFLBG glue solution when preparing the positive electrode, coating a 0.5-mu m PVDFLBG glue layer on the PI film, and drying to obtain a PI film, thus finally obtaining the sulfide all-solid-state battery cell.
Example 9
Example 9 differs from example 1 in that,
and the thickness of the PVDF-HFP adhesive layer on the PI membrane is 0.8 mu m, and finally the sulfide all-solid-state battery cell is obtained.
Example 10
Example 10 differs from example 1 in that,
and the thickness of the PVDF-HFP adhesive layer on the PI membrane is 1 mu m, and finally the sulfide all-solid-state battery cell is obtained.
Example 11
Example 11 differs from example 1 in that,
and the thickness of the PVDF-HFP adhesive layer on the PI membrane is 1.2 mu m, and finally the sulfide all-solid-state battery cell is obtained.
Example 12
Example 12 differs from example 1 in that,
and the thickness of the PVDF-HFP adhesive layer on the PI membrane is 0.4 mu m, and finally the sulfide all-solid-state battery cell is obtained.
Example 13
Example 13 differs from example 1 in that,
inserting 4 x 4.5cm PI film with thickness of 100 μm into the middle of 2 above all solid state unit cells, stacking, packaging, holding at 120deg.C for 60min under 10MPa, isostatic pressing for five times, unpacking, welding tab, and packaging to obtain sulfide all solid state cell.
Example 14
Example 14 differs from example 1 in that,
inserting 4 x 4.5cm PI film with thickness of 100 μm into the middle of 2 above all solid state unit cells, stacking, packaging, holding at 100MPa and 40 deg.C for 1min, isostatic pressing for five times, unpacking, welding tab, packaging, and packaging to obtain sulfide all solid state cell.
Comparative example 1
Comparative example 1 differs from example 1 in that,
and directly overlapping, stacking and packaging the 2 all-solid-state unit cells, then unsealing, welding and packaging the electrode lugs to complete assembly, and finally obtaining the sulfide all-solid-state cell. The battery is short-circuited under the pressure of 10MPa, and the discharge gram capacity of the battery is 45% of the discharge gram capacity of 0.1 ℃ under the pressure of 2MPa and 25 ℃ and 1 ℃.
The sulfide all-solid state battery cells obtained in examples 1 to 14 and comparative example 1 above were each tested for a percentage of 0.1C discharge gram capacity at 1C under a pressure of 10MPa at 25C using a battery holder, and the test results are shown in table 1.
TABLE 1
Implementation/pairingProportion of The discharge gram capacity at 1C is 0.1C as a percentage/%
Example 1 68.8
Example 2 67.0
Example 3 69.1
Example 4 68.0
Example 5 67.0
Example 6 63.5
Example 7 63.0
Example 8 68.0
Example 9 67.6
Example 10 68.5
Example 11 62.2
Example 12 63.0
Example 13 67.0
Example 14 67.5
Comparative example 1 45.0
As can be seen from the data in table 1 above, the data of examples 1 to 14 are all significantly better than the data of comparative example 1. That is, compared with comparative example 1, the sulfide all-solid state cells of examples 1 to 14 have higher rate capability, which means that examples 1 to 14 have lower internal resistance than the sulfide all-solid state cell of comparative example 1, and the high pressure maintaining pressure applied to the sulfide all-solid state cell is beneficial to reducing the internal resistance of the sulfide all-solid state cell, so that the sulfide all-solid state cells of examples 1 to 14 have higher rate capability under the same pressure maintaining condition, which means that the sulfide all-solid state cells of examples 1 to 14 can bear higher pressure, that is, the application can offset at least part of shear force inside the all-solid state cell by the polymer membrane, and reduce the transmission of the shear force inside the all-solid state cell to the inside of the all-solid state cell and the adjacent all-solid state cell, thereby enabling the obtained sulfide all-solid state cell to resist internal high shear force, and further solving the technical problems of the application.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
because the sulfide all-solid-state battery cell comprises the polymer membrane overlapped with the all-solid-state unit battery cell, the polymer membrane can offset at least partial shearing force in the all-solid-state unit battery cell, and the shearing force born by the inside of the all-solid-state unit battery cell is relieved, so that the shearing force is reduced to be transmitted to the inside of the all-solid-state unit battery cell and the adjacent all-solid-state unit battery cell, the interface impedance is reduced, and further, internal short circuit failure caused by high shearing force damage and current collector curling interference between the adjacent all-solid-state unit battery cells under the high pressure condition is prevented, and further, the capacity of the sulfide all-solid-state battery cell can be realized by adjusting the quantity of the all-solid-state unit battery cells, and the consistency and the safety of the high-capacity sulfide all-solid-state battery cell are effectively increased.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

1. A sulfide all-solid-state battery cell is characterized by comprising all-solid-state unit battery cells and polymer films which are alternately stacked, wherein the all-solid-state unit battery cells and the polymer films are bonded through adhesive layers,
the all-solid-state unit cell comprises a first positive electrode, a first electrolyte layer, a double-sided negative electrode, a second electrolyte layer and a second positive electrode which are sequentially stacked;
the distance between the projection edge of the double-sided negative electrode on the polymer membrane and the edge of the polymer membrane is less than or equal to 1mm, and the projection area of the double-sided negative electrode on the polymer membrane is less than or equal to the area of the polymer membrane;
the thermal expansion coefficient of the polymer film sheet is 2×10 -5 ~3×10 -6 Between every two DEG C, the Young's modulus of the polymer membrane is not less than 1Gpa;
the polymer membrane is selected from one or more of PC membrane, PET membrane, PMMA membrane, PI membrane and PP membrane, and the thickness of the polymer membrane is 10 μm-1 mm.
2. The sulfide all-solid-state battery cell according to claim 1, wherein the thickness of the polymer membrane is between 30 and 100 μm.
3. The sulfide all-solid state cell of claim 1, wherein the glue layer is selected from any one or more of PVDF-HFP glue layer, PVDFLBG glue layer, PVDF glue layer, SBR glue layer, SBS glue layer, SEBS glue layer, NBR glue layer, HNBR glue layer.
4. The sulfide all-solid state battery cell according to claim 3, wherein the thickness of the adhesive layers is 0.5-1 μm each independently.
5. A sulfide all-solid state battery cell as claimed in any one of claims 1 to 4, wherein,
the first positive electrode comprises a first positive electrode current collector and a first positive electrode active layer which are overlapped, and the first positive electrode active layer is in contact with the first electrolyte layer;
the second positive electrode comprises a second positive electrode current collector and a second positive electrode active layer which are stacked, and the second positive electrode active layer is in contact with the second electrolyte layer.
6. The sulfide all-solid state battery cell according to claim 5, wherein the first positive electrode active layer and the second positive electrode active layer each independently include a positive electrode active material having a chemical formula LiNi x Co y M z O 2 Wherein x is greater than or equal to 0, y is greater than or equal to 0, z is greater than or equal to 0, and x+y+z=1, wherein M is selected from any one or more of Mn, al, zr, ti, V, mg, fe, mo.
7. The sulfide all-solid state battery cell according to claim 6, wherein a coating layer is provided outside the positive electrode active material, and the coating layer is an ion conductor material.
8. The sulfide all-solid state battery cell according to claim 7, whereinWherein the ion conductor material is selected from Li 2 TiO 3 、LiNbO 3 、Li 3 BO 3 、Li 2 ZrO 3 、LiPO 3 、Li 2 MnO 4 、Al(PO 3 ) 3 、La(PO 3 ) 3 、NaPO 3 Any one or more of the following.
9. The sulfide all-solid-state battery cell according to claim 7, wherein the thickness of the coating layer is 1-10 nm.
10. The sulfide all-solid state battery cell according to any one of claims 1 to 4, wherein the double-sided anode includes an anode current collector and anode active layers provided on opposite surfaces of the anode current collector, one of the anode active layers being provided in contact with the first electrolyte layer, and the other anode active layer being provided in contact with the second electrolyte layer.
11. The sulfide all-solid state battery cell according to claim 10, wherein the two anode active layers each independently include an anode material selected from any one of a Si alloy anode active material, a carbon material.
12. The sulfide all-solid state battery cell according to claim 11, wherein the Si alloy anode active material includes any one or more of a solid solution of any one or more of Fe, co, sb, bi, pb, ni, cu, zn, ge, in, sn or Ti and silicon, silicon oxide, silicon carbide, silicon nitride.
13. The sulfide all-solid state battery cell of claim 11, wherein the carbon material is selected from any one or more of hard carbon, soft carbon, and graphite.
14. The sulfide all-solid state battery of any one of claims 1 to 4, wherein the areas of the first positive electrode and the second positive electrode are each independently smaller than the area of the double-sided negative electrode, the areas of the first electrolyte layer and the second electrolyte layer are each independently larger than the area of the first positive electrode or the second positive electrode, and the areas of the first electrolyte layer and the second electrolyte layer are each independently smaller than or equal to the area of the double-sided negative electrode.
15. A method of making the sulfide all-solid state cell of any one of claims 1 to 4, the method comprising:
and carrying out isostatic pressing compounding on the all-solid-state unit battery core and the polymer membrane to obtain the sulfide all-solid-state battery core.
16. The method according to claim 15, wherein the isostatic compounding is performed at a temperature of 40-120 ℃, a pressure of 10-100 mpa, a dwell time of 1-60 min, and a number of pressing times of 1-5 times.
17. An all-solid-state lithium ion battery comprising a cell, characterized in that the cell is a sulfide all-solid-state cell according to any one of claims 1 to 14.
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