CN115425287A - All-solid-state battery containing alloy type negative electrode and elastic electrolyte - Google Patents
All-solid-state battery containing alloy type negative electrode and elastic electrolyte Download PDFInfo
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- CN115425287A CN115425287A CN202211207102.1A CN202211207102A CN115425287A CN 115425287 A CN115425287 A CN 115425287A CN 202211207102 A CN202211207102 A CN 202211207102A CN 115425287 A CN115425287 A CN 115425287A
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- 239000011701 zinc Substances 0.000 description 1
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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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- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention relates to an all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte, which consists of the alloy type negative electrode, the elastic electrolyte and a positive electrode; the elastomeric electrolyte comprises an elastomeric polymer matrix and a metal salt, optionally including a plasticizer; wherein the content of the elastic polymer is 20-95 wt.%, the content of the metal salt is 5-50 wt.%, and the content of the plasticizer is 0-50 wt.%; the elastic electrolyte has an ionic conductivity of (0.5-100.0) x 10 ‑4 S cm ‑1 The thickness is 5-1000 μm, and the elastic deformation is 50-500%. Elastic electrolyte dynamic self-adaptive alloy type negative electrodeThe volume shrinkage/expansion in the electrode charging and discharging process ensures good interface contact between the electrolyte and the negative electrode, solves the problem of continuous attenuation of the capacity of the alloy type negative electrode solid-state battery caused by insufficient and unstable interface contact, and improves the cycle performance of the alloy type negative electrode solid-state battery.
Description
Technical Field
The invention belongs to the field of solid-state batteries, and relates to an all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte.
Background
The alloy type negative electrode has higher theoretical specific capacity than the traditional intercalation type negative electrode, and can be used for constructing high-specific-energy primary batteries and secondary batteries. Taking a silicon negative electrode as an example, the theoretical specific capacity of the silicon negative electrode as a negative electrode material of a lithium ion battery is 3759mAh g -1 (Li 15 Si 4 ) A commercial graphite negative electrode (372 mAh g) -1 ) 10 times higher than the desired value. The theoretical energy density of the lithium ion battery taking silicon as the cathode material can reach 400Wh kg -1 And has good application prospect in the fields of electric vehicles and large-scale energy storage. However, the alloy-type negative electrode undergoes a large volume expansion during the charging and discharging processes (for example, the volume expansion of the silicon negative electrode during the lithium storage process can reach more than 300%), and the material is crushed by the large volume effect, so that the alloy-type negative electrode and the organic electrolyte solution continuously undergo side reactions, an unstable Solid Electrolyte Interface (SEI) is generated, the alloy-type negative electrode irreversibly loses electrical contact, and the rapid deterioration of cycle performance hinders the practical application of the alloy-type negative electrode.
The current methods for improving the cycling stability of the alloy type negative electrode comprise nanocrystallization, carbon compounding, adhesive modification and electrolyte modification. Among them, modification of the electrolyte can fundamentally improve the structural stability of SEI, and is considered to be the most effective modification method of an alloy-type negative electrode. Different from electrolyte, the use of the solid electrolyte can obviously reduce the interface of the lithium-silicon alloy/electrolyte, effectively inhibit the formation of SEI, simultaneously slow down the continuous increase of new SEI caused by volume expansion of the cathode, and improve the cycling stability of the alloy cathode. However, both inorganic solid electrolytes and conventional polymer electrolytes have the problem of insufficient solid-solid interface contact with an alloy type negative electrode, and cannot effectively relieve the huge volume effect of the alloy zinc negative electrode in the charge-discharge cycle process, so that the cycle life, the energy density and the power density of a solid-state full battery are reduced. The above problems also hinder the commercial application of high-performance solid-state batteries based on alloy-type negative electrodes.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides an all-solid battery including an elastic electrolyte and an alloy-type negative electrode. And tightly pressing the elastic electrolyte, the alloy type negative electrode and the alloy type positive electrode to obtain the all-solid-state battery. The elastic electrolyte has an excessively large deformation amount, and the elastic modulus thereof is significantly higher than that of common solid polymer electrolytes, inorganic solid electrolytes and liquid electrolytes. The alloy type negative electrode expands in the lithium embedding process, and the elastic electrolyte tightly combined with the alloy type negative electrode is compressed, so that the influence of the expansion of the alloy type negative electrode on the internal pressure of the solid-state battery can be relieved. The volume of the alloy type negative electrode shrinks in the lithium removing process, and the elastic electrolyte tightly combined with the alloy type negative electrode expands under reduced pressure, so that the interface contact problem caused by the shrinkage of the alloy type negative electrode can be relieved. In conclusion, the elastic electrolyte can make dynamic self-adaptive adjustment on volume shrinkage/expansion caused by the lithium desorption process of the alloy type cathode, and solves the problem that the interface contact of the alloy type cathode/lithium guide layer is unstable in the operation process of the solid-state battery, so that the capacity attenuation of the alloy type cathode solid-state battery is slowed down, the cycle performance of the alloy type cathode solid-state battery is improved, and the alloy type cathode solid-state battery is further assembled with a positive electrode material to obtain an all-solid-state battery with high capacity, long service life and stable cycle.
The technical purpose of the invention is realized by the following technical scheme:
an all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte comprises the alloy type negative electrode, the elastic electrolyte and a positive electrode.
In a preferred embodiment of the present invention, the alloy type negative electrode is fixed to a current collector side surface, and the elastic electrolyte is located between the negative electrode and the positive electrode.
In a preferred embodiment of the present invention, the all-solid-state battery is selected from primary or secondary batteries; further, the all-solid-state battery is any one selected from a lithium battery, a sodium battery, a potassium battery, a magnesium battery, a calcium battery and an aluminum battery.
In a preferred embodiment of the present invention, the alloy type negative electrode includes a metal/nonmetal capable of forming an alloy with a metal ion and a compound thereof; further, the metal ions are any one of lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions and aluminum ions.
In a preferred embodiment of the present invention, the elastic electrolyte is tightly combined with the alloy type negative electrode and the alloy type positive electrode in an in-situ or ex-situ manner; further, the combination method comprises any one of the following modes:
(1) The elastic electrolyte is pre-cured and then coated on one side of the alloy type cathode to continue to finish curing;
(2) The elastic electrolyte is pre-cured and then coated on one side of the alloy type negative electrode, and is attached to the positive electrode, and then curing is continuously completed;
(3) And injecting a precursor solution of the elastic electrolyte between the alloy type negative electrode and the positive electrode, and finishing solidification.
In a preferred embodiment of the invention, the elastomeric electrolyte comprises an elastomeric polymer matrix and a metal salt; optionally, the elastomeric electrolyte further comprises a plasticizer; wherein the content of the elastic polymer is 30-85 wt.%, the content of the lithium salt is 5-50 wt.%, and the content of the plasticizer is 0-50 wt.%.
In a preferred embodiment of the present invention, the elastomeric polymer matrix comprises one or more of a thermoset elastomer, a thermoplastic elastomer, or a copolymer or blend based on the thermoset/thermoplastic elastomer; further, the thermosetting elastomer is selected from one or more of natural rubber, isoprene rubber, polybutadiene rubber, styrene butadiene rubber, nitrile butadiene rubber and chloroprene rubber; the thermoplastic elastomer is selected from one or more of hydrogenated ethylene-butylene rubber, polyamide, vinyl acetate, polyolefin and polyurethane.
In a preferred embodiment of the present invention, the metal salt comprises one or more of an inorganic salt and an organic salt; further, the inorganic salt is selected from one or more of perchlorate, tetrafluoroborate, hexafluoroarsenate and hexafluorophosphate, and the organic salt is selected from one or more of bisoxalato borate, difluorooxalato borate, bisdifluorosulfonimide and bistrifluoromethylsulfonimide. The metal ions of the metal salt in the electrolyte can conduct through the electrolyte and act as carriers for the solid-state battery,
in a preferred embodiment of the present invention, the plasticizer in the electrolyte comprises one or more of organic molecules such as alcohol, phenol, ether, acid, aldehyde, ketone, ester, nitrile, amine, and ionic liquid. In addition, the plasticizer can promote the metal ion carrier transmission of the elastic electrolyte molecular chain, and part of the plasticizer can generate a cross-linking reaction with the elastic electrolyte molecular chain, so that the mechanical property of the elastic electrolyte is improved.
In a preferred embodiment of the present invention, the elastic electrolyte has an ionic conductivity of 0.5 x 10 -4 ～100.0×10 -4 S cm -1 The thickness is 5-1000 μm, the elastic deformation is 50-500%, and the flame retardant property is provided.
Compared with the prior art, the invention has the following beneficial effects:
1. in the aspect of battery assembly process, the three assembly modes adopted by the invention have simple process and good modification effect. The elastic electrolyte is pre-cured and then is continuously cured on the surface of the alloy type negative electrode, so that the bonding tightness of the elastic electrolyte and the alloy type negative electrode can be improved, the elastic electrolyte can be enabled to be super-conformal with the alloy type negative electrode in the lithium releasing and embedding process, the interface impedance between the elastic electrolyte and the alloy type negative electrode is reduced, and the cycle life of the solid alloy type negative electrode battery is prolonged. The anode is attached to the pre-cured elastic electrolyte and then is cured, so that the bonding tightness of the anode and the elastic electrolyte can be improved, the interface impedance between the anode and the elastic electrolyte is reduced, and the capacity of the alloy type cathode solid-state battery is improved. The elastic electrolyte is solidified between the alloy type negative electrode and the positive electrode in situ and in the pores of the two electrodes, and the elastic electrolyte is bound on the surface of the alloy type negative electrode particles in the process of lithium intercalation and deintercalation of the alloy type negative electrode, so that the transportation of lithium ions in the alloy type negative electrode and the positive electrode is promoted, and the cycle performance of the alloy type negative electrode solid-state battery is improved.
2. In terms of battery performance, the elastic electrolyte adopted in the solid-state battery designed by the invention has an overlarge deformation amount, and the elastic modulus of the elastic electrolyte is remarkably higher than that of common solid-state polymer electrolytes, inorganic solid-state electrolytes and liquid electrolytes. The elastic electrolyte has an ultra-large deformation amount, can dynamically and self-adapt to the obvious volume shrinkage/expansion of the alloy type cathode in the charging and discharging processes, and ensures the close contact between the elastic electrolyte and the alloy type cathode, thereby slowing down the capacity attenuation of the alloy type cathode solid-state battery and improving the cycle performance of the solid-state alloy type cathode battery.
3. In terms of battery safety, the invention designs an all-solid-state battery containing an elastic electrolyte and an alloy type negative electrode. And tightly pressing the elastic electrolyte, the alloy type negative electrode and the alloy type positive electrode to obtain the all-solid-state battery. The all-solid-state battery has flame retardance and excellent mechanical properties, and the adopted alloy type cathode has higher capacity than the traditional insertion layer type cathode and higher safety than a metal lithium cathode. Therefore, the all-solid battery designed by the invention has better safety than the traditional solid electrolyte battery or liquid electrolyte battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of the cell structure;
FIG. 2 is a stress strain curve of the elastic electrolyte prepared in example 1 of the present invention;
FIG. 3 flame retardant properties of the elastomeric electrolyte prepared in example 1 of the present invention;
FIG. 4 ion conductivity of the elastic electrolyte prepared in example 1 of the present invention;
FIG. 5 shows the performance of a symmetric cell with an elastic electrolyte of lithium prepared in example 1 of the present invention;
fig. 6 shows the full cell performance of the assembly of the elastic electrolyte, the silicon negative electrode and the lithium iron phosphate positive electrode prepared in example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of xylene in a completely sealed 20ml sample bottle, stirring for 6 hours on a hot bench at 60 ℃ at a rotating speed of 500r/min, and transferring the sample bottle to a glove box in an argon atmosphere; adding 0.1875g of lithium bis (trifluoromethyl) sulfonyl imide into a glove box, sealing, taking out, and continuously stirring on a hot table at 60 ℃ for 12 hours; and cooling to room temperature, taking out the colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out blade coating by using a scraper with the diameter of 750 mu m to obtain a flat and uniform electrolyte liquid film, volatilizing and drying at room temperature for 8 hours, transferring the electrolyte liquid film into a vacuum drying oven, and curing at the temperature of 60 ℃ and the pressure of-0.1 MPa for 12 hours to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state lithium battery containing the alloy cathode and the elastic electrolyte.
Example 2 (nitrile rubber instead of polyurethane)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of polyurethane, dissolving the polyurethane in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring for 6 hours on a hot bench at 60 ℃ at a rotating speed of 500r/min, and transferring the sample bottle to a glove box in an argon atmosphere; adding 0.1875g of lithium bis (trifluoromethyl) sulfonyl imide into a glove box, sealing, taking out, and continuously stirring on a hot bench at 60 ℃ for 12 hours; and cooling to room temperature, taking out the colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out blade coating by using a scraper with the diameter of 750 mu m to obtain a flat and uniform electrolyte solution film, volatilizing and drying at room temperature for 8 hours, transferring the electrolyte solution into a vacuum drying oven, and curing at the temperature of 60 ℃ and the pressure of-0.1 MPa for 12 hours to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 3 (lithium bistrifluoromethylsulfonyl imide replaced by lithium perchlorate)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a hot bench at the temperature of 60 ℃ at the rotating speed of 500r/min, and transferring the sample bottle to a glove box in an argon atmosphere; adding 0.1875g of lithium perchlorate into a glove box, sealing, taking out, and continuously placing on a hot bench at 60 ℃ to stir for 12 hours; and cooling to room temperature, taking out the colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out blade coating by using a scraper with the diameter of 750 mu m to obtain a flat and uniform electrolyte liquid film, volatilizing and drying at room temperature for 8 hours, transferring the electrolyte liquid film into a vacuum drying oven, and curing at the temperature of 60 ℃ and the pressure of-0.1 MPa for 12 hours to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 4 (varying Polymer content)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.75g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring for 6 hours on a hot bench at 60 ℃ at a rotating speed of 500r/min, and transferring the sample bottle to a glove box in an argon atmosphere; adding 0.1875g of lithium perchlorate into a glove box, sealing, taking out, and continuously placing on a hot bench at 60 ℃ to stir for 12 hours; and cooling to room temperature, taking out the colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out blade coating by using a scraper with the diameter of 750 mu m to obtain a flat and uniform electrolyte liquid film, volatilizing and drying at room temperature for 8 hours, transferring the electrolyte liquid film into a vacuum drying oven, and curing at the temperature of 60 ℃ and the pressure of-0.1 MPa for 12 hours to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 5 (salt content changed to 50%)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot bench at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.375g of lithium bis (trifluoromethyl) sulfonyl imide into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on a 60 ℃ hot bench, stirring the glove box for 12 hours, cooling the glove box to room temperature, taking out a colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out blade coating by using a 750 mu m scraper to obtain a flat and uniform electrolyte membrane, volatilizing and drying the electrolyte membrane for 8 hours at room temperature, transferring the electrolyte membrane to a vacuum drying box, and curing the electrolyte for 12 hours at the temperature of 60 ℃ and the pressure of-0.1 MPa to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 6 (fluoroethylene carbonate as plasticizer, content 10 wt.%)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot table at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.1875g of lithium bis (trifluoromethyl) sulfimide into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on a 60 ℃ hot table, stirring the glove box for 12 hours, taking out a colloid in the sample bottle after the temperature is reduced to room temperature, placing the colloid on a clean glass plate, scraping the colloid on the clean glass plate by using a 750 mu m scraper to obtain a flat and uniform electrolyte membrane, volatilizing and drying the electrolyte membrane for 8 hours at room temperature, transferring the electrolyte membrane into a vacuum drying box, curing the electrolyte membrane for 12 hours under the conditions of 60 ℃, swelling at-0.1 MPa, transferring the colloid into the glove box, and obtaining 10wt.% of fluoroethylene carbonate to obtain the elastic electrolyte
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 7 (fluoroethylene carbonate as plasticizer, content 20 wt.%)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot bench at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.1875g of lithium bis (trifluoromethyl) sulfimide into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on a 60 ℃ hot bench, stirring the glove box for 12 hours, taking out a colloid in the sample bottle after the temperature is reduced to room temperature, placing the colloid on a clean glass plate, performing scraping with a 750 mu m scraper to obtain a flat and uniform electrolyte membrane, volatilizing and drying the electrolyte membrane for 8 hours at room temperature, transferring the electrolyte membrane into a vacuum drying box, curing the electrolyte membrane for 12 hours at the temperature of 60 ℃ and under the pressure of 0.1MPa, transferring the electrolyte membrane into the glove box, and swelling 20wt.% of fluoroethylene carbonate to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the elastic electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 8 (technical solution replacement for in-situ combination of positive electrode)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot bench at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.1875g of lithium bis (trifluoromethyl) sulfimide into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on the 60 ℃ hot bench, stirring the glove box for 12 hours, cooling the glove box to room temperature, taking out a colloid in the sample bottle, placing the colloid on a dry lithium iron phosphate anode plate, scraping the colloid on the anode by using a 750 mu m scraper to obtain a flat and uniform electrolyte liquid film on the surface of the anode, volatilizing and drying the colloid for 8 hours at room temperature, transferring the colloid into a vacuum drying box, and curing the colloid for 12 hours under the conditions of 60 ℃ and-0.1 MPa to obtain the in-situ combined elastic electrolyte-anode.
And packaging the in-situ combined electrolyte and the lithium iron phosphate anode with the silicon cathode to obtain the all-solid-state battery containing the alloy type cathode and the elastic electrolyte.
Example 9 (technical solution is changed to in-situ combination cathode)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot bench at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.1875g of lithium bis (trifluoromethyl) sulfimide into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on a 60 ℃ hot bench, stirring the glove box for 12 hours, cooling the mixture to room temperature, taking out a colloid in the sample bottle, placing the colloid on a dried silicon negative electrode plate, carrying out blade coating on the negative electrode by using a 750 mu m scraper to obtain a flat and uniform electrolyte film on the surface of the negative electrode plate, volatilizing and drying the colloid for 8 hours at the room temperature, transferring the colloid into a vacuum drying box, and curing the colloid for 12 hours under the conditions of 60 ℃ and 0.1MPa to obtain the in-situ bonded elastic electrolyte-positive electrode.
And packaging the in-situ combined electrolyte and the silicon cathode together with the lithium iron phosphate anode to obtain the all-solid-state battery containing the alloy cathode and the elastic electrolyte.
Example 10 (phosphorus negative electrode instead of silicon negative electrode, lithium bis (trifluoromethyl) sulfonimide instead of sodium bis (trifluoromethyl) sulfonimide)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot bench at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.1875g of bis (trifluoromethyl) sulfimide sodium into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on a 60 ℃ hot bench, stirring the glove box for 12 hours, cooling the mixture to room temperature, taking out the colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out scraping with a 750 mu m scraper to obtain a flat and uniform electrolyte membrane, volatilizing and drying the electrolyte membrane for 8 hours at room temperature, transferring the electrolyte membrane into a vacuum drying box, and curing the electrolyte membrane for 12 hours at the temperature of 60 ℃ and the pressure of 0.1MPa to obtain the elastic electrolyte.
And sequentially combining and packaging the phosphorus cathode, the elastic electrolyte and the sodium vanadium phosphate anode in a 2032 type button battery to obtain the all-solid-state lithium battery containing the alloy cathode and the elastic electrolyte.
Example 11 (NCM 523 positive electrode instead of lithium iron phosphate positive electrode)
An all-solid-state battery containing an alloy type negative electrode and an elastic electrolyte has the technical scheme that:
weighing 0.375g of nitrile rubber, dissolving the nitrile rubber in a mixed solution of 1.25ml of acetone and 2.5ml of dimethylbenzene in a completely sealed 20ml sample bottle, stirring the mixture for 6 hours on a 60 ℃ hot bench at a rotating speed of 500r/min, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.1875g of lithium bis (trifluoromethyl) sulfimide into the glove box, sealing the glove box, taking out the glove box, continuously placing the glove box on a 60 ℃ hot bench, stirring the glove box for 12 hours, cooling the mixture to room temperature, taking out the colloid in the sample bottle, placing the colloid on a clean glass plate, carrying out blade coating by using a 750 mu m scraper to obtain a flat and uniform electrolyte membrane, volatilizing and drying the electrolyte membrane for 8 hours at room temperature, transferring the electrolyte membrane into a vacuum drying box, and curing the electrolyte membrane for 12 hours under the conditions of 60 ℃ and 0.1MPa to obtain the elastic electrolyte.
And sequentially combining and encapsulating the silicon negative electrode, the elastic electrolyte and the NCM523 positive electrode in a 2032 type button battery to obtain the all-solid-state lithium battery containing the alloy negative electrode and the elastic electrolyte.
Comparative example 1:
an all-solid-state battery based on inelastic PEO adopts the technical scheme that:
weighing 0.44g of PEO, dissolving the PEO in 10ml of acetonitrile solution in a completely sealed 20ml sample bottle, stirring the solution at room temperature at a rotating speed of 500r/min for 6 hours, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.22g of lithium bis (trifluoromethyl) sulfonyl imide into the glove box, sealing the glove box, taking out the sample bottle, continuously stirring the sample bottle on a stirring table at room temperature for 12 hours, taking out the colloid in the sample bottle by using a rubber head dropper, placing the colloid in a polytetrafluoroethylene mold with the diameter of 14cm, volatilizing and drying the colloid for 8 hours at room temperature, transferring the colloid into a vacuum drying box, and drying the colloid for 12 hours at the temperature of 60 ℃ and under the pressure of-0.1 MPa to obtain the PEO solid electrolyte.
And sequentially combining and packaging the silicon cathode, the PEO-based electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state lithium battery.
Comparative example 2:
an all-solid-state battery based on inelastic PEO adopts the technical scheme that:
weighing 0.44g of PEO, dissolving the PEO in 10ml of acetonitrile solution in a completely sealed 20ml sample bottle, stirring for 6 hours at a rotating speed of 500r/min at room temperature, transferring the sample bottle to a glove box in an argon atmosphere, adding 0.22g of lithium bis (trifluoromethyl) sulfonyl imide into the glove box, sealing, taking out, continuously stirring for 12 hours at room temperature on a stirring table, taking out the colloid in the sample bottle by using a rubber head dropper, placing the colloid in a polytetrafluoroethylene mold with the diameter of 14cm, volatilizing and drying for 8 hours at room temperature, drying for 12 hours at the conditions of 60 ℃, minus 0.1MPa, transferring the colloid into the glove box, and swelling 10wt.% of fluoroethylene carbonate to obtain the elastic electrolyte.
And sequentially combining and packaging the silicon cathode, the PEO-based electrolyte and the lithium iron phosphate anode in a 2032 type button battery to obtain the all-solid-state lithium battery.
Experimental example 1:
the results of the basic tests carried out on the elastic electrolytes prepared in examples 1 to 7 are shown in Table 1:
TABLE 1 basic test data of the elastic electrolytes prepared in examples 1 to 7 and comparative examples 1 to 2
Experimental example 2:
the elastic electrolyte prepared in examples 1 to 7 was cut into disks with a diameter of 16cm, and assembled with lithium metal/sodium metal to form a Li (Na) symmetrical battery, wherein the diameter of the metal electrode was 14cm, and the button-type symmetrical battery was designated as CR2032. At 0.1mA cm -2 Current density, 0.1mAh cm -2 Electric quantity is a test condition, and a symmetric battery long cycle test is carried out at 60 ℃. The test results are shown in table 2.
TABLE 2 data of long cycle test of symmetric cells for examples 1-7 and comparative examples 1-2
Experimental example 3:
the all-solid-state batteries containing the alloy type negative electrodes and the elastic electrolyte obtained in the examples 1 to 11 were subjected to the rate and long cycle tests, wherein the voltage window of the lithium ion battery was 2.5 to 4.5V, and the voltage window of the sodium ion battery was 2.7 to 4.2V. The multiplying power test current density is selected in sequence as follows: 0.1C, 0.2C, 0.3C, 0.4C and 0.5C, the long-cycle test current density is 0.2C, the battery test is carried out at the temperature of 60 ℃, and the experimental results are shown in Table 3:
table 3 data of rate and long cycle tests performed on all-solid-state batteries of examples 1 to 11 and comparative examples 1 to 2
As is apparent from the results in table 1, the electrolyte is significantly superior to conventional PEO-based solid electrolytes in terms of ion conductivity, mechanical properties, and flame retardant properties, and it is known that the ion conductivity and elastic modulus of the solid electrolyte are mutually restricted, and the mass fraction of the elastic polymer monomer is 40-70%, so that the electrolyte can be provided with excellent elastic modulus and higher ion conductivity; under the condition that 30-60% of mass fraction of plasticizer is added, acting force between polymer chain segments is weakened, molecular chain motion is enhanced, so that the electrolyte realizes great improvement of ionic conductance, and the electrolyte still maintains higher elastic modulus based on the intrinsic excellent elastic modulus of the elastomer. The results in table 1 show that, within the limited range of results of orthogonal experiments, the weight ratio of the elastic polymer to the lithium salt is 2.
The symmetric, full cell data of tables 2, 3 fully confirm the above conclusions. Compared with the solid electrolyte reported at present, the solid electrolyte prepared by the method has more excellent mechanical and electrochemical properties.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. An all-solid-state battery containing an alloy-type negative electrode and an elastic electrolyte is characterized by comprising the alloy-type negative electrode, the elastic electrolyte and a positive electrode.
2. The all-solid battery according to claim 1, wherein the alloy-type negative electrode is fixed to a current collector side, and the elastic electrolyte is located between the negative electrode and the positive electrode.
3. The all-solid battery according to claim 1, wherein the all-solid battery is selected from a primary or secondary battery; further, the all-solid-state battery is any one of a lithium battery, a sodium battery, a potassium battery, a magnesium battery, a calcium battery and an aluminum battery.
4. The all-solid battery according to claim 1, wherein the alloy type negative electrode includes a metal/nonmetal capable of forming an alloy with a metal ion and a compound thereof; further, the metal ions are any one of lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions and aluminum ions.
5. The all-solid battery according to claim 1, wherein the elastic electrolyte is tightly combined with the alloy type negative electrode and the alloy type positive electrode in an in-situ or ex-situ manner; further, the combination method comprises any one of the following modes:
(1) The elastic electrolyte is pre-cured and then coated on one side of the alloy type cathode to continue to finish curing;
(2) The elastic electrolyte is pre-cured and then coated on one side of the alloy type negative electrode, and is attached to the positive electrode, and then curing is continuously completed;
(3) And injecting a precursor solution of the elastic electrolyte between the alloy type negative electrode and the positive electrode, and completing solidification.
6. The all-solid battery according to claim 1, wherein the elastic electrolyte includes an elastic polymer matrix and a metal salt; optionally, the elastomeric electrolyte further comprises a plasticizer; wherein the content of the elastic polymer is 30-85 wt.%, the content of the lithium salt is 5-50 wt.%, and the content of the plasticizer is 0-50 wt.%.
7. The all-solid battery according to claim 1, wherein the elastic polymer matrix comprises one or more of a thermosetting elastomer, a thermoplastic elastomer, or a copolymer or mixture based on the thermosetting/thermoplastic elastomer; further, the thermosetting elastomer is selected from one or more of natural rubber, isoprene rubber, polybutadiene rubber, styrene butadiene rubber, nitrile butadiene rubber and chloroprene rubber; the thermoplastic elastomer is selected from one or more of hydrogenated ethylene-butylene rubber, polyamide, vinyl acetate, polyolefin and polyurethane.
8. The all-solid battery according to claim 1, wherein the metal salt includes one or more of an inorganic salt, an organic salt; further, the inorganic salt is selected from one or more of perchlorate, tetrafluoroborate, hexafluoroarsenate and hexafluorophosphate, and the organic salt is selected from one or more of bisoxalato borate, difluorooxalato borate, bisdifluorosulfonimide and bistrifluoromethylsulfonyl imide.
9. The all-solid battery according to claim 1, wherein the plasticizer in the electrolyte includes one or more of organic molecules such as alcohol, phenol, ether, acid, aldehyde, ketone, ester, nitrile, amine, and ionic liquid.
10. The all-solid battery according to claim 1, wherein the elastic electrolyte has an ionic conductivity of 0.5 x 10 -4 ～100.0×10 -4 S cm -1 The thickness is 5-1000 μm, the elastic deformation is 50-500%, and the flame retardant property is provided.
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| US20220190346A1 (en) * | 2020-12-14 | 2022-06-16 | Global Graphene Group, Inc. | Lithium-protecting polymer composite layer for a lithium metal secondary battery and manufacturing method |
| CN114824336A (en) * | 2021-01-18 | 2022-07-29 | 本田技研工业株式会社 | Solid-state battery and solid-state battery cell |
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| US20200099090A1 (en) * | 2017-05-26 | 2020-03-26 | Beijing Normal University | Flexible all-solid-state lithium-ion secondary battery and preparation method thereof |
| CN107785609A (en) * | 2017-10-31 | 2018-03-09 | 江汉大学 | The preparation method of full solid state polymer electrolyte and the serondary lithium battery containing the electrolyte |
| KR20210074811A (en) * | 2019-12-12 | 2021-06-22 | 한국에너지기술연구원 | Composite Electrode for All-Solid-State Battery and Method Of Manufacturing The Same |
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