CN113224371A - High-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery - Google Patents
High-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery Download PDFInfo
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Abstract
The invention provides a high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery, and relates to the technical field of batteries. Step one, preparing a battery anode material, adding a hydrogen peroxide solution into vanadium pentoxide, violently stirring the mixture to obtain vanadium sol, and respectively adding ionic water and polyethylene glycol into the obtained vanadium sol. The core-shell structure with large-area contact interface and stable structural strength of the anode internal structure can remarkably increase ion/electron transmission and buffer liquid volume change during circulation, and effective interface engineering enables SSLB to have lower interface resistance, high capacity and good circulation stability, and for complex reaction of the cathode interface and the problems of lithium dendrite growth and volume expansion, the former can be avoided by adopting a solid electrolyte method, and the latter can guide lithium ion deposition and promote stable circulation of a lithium metal cathode by adding a copper-nickel double metal layer modified three-dimensional framework material into the cathode.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative-electrode composite solid-state lithium battery.
Background
In recent years, lithium batteries have received extensive attention due to high energy density and long cycle life, but safety problems and limited energy density are two main problems faced by current liquid lithium batteries, safe solid electrolyte batteries are gradually the first choice, but poor interfacial wettability of solid electrolyte hinders lithium ion transmission, affects service life and energy density of lithium batteries, lithium metal is used as a negative electrode instead of graphite, energy density of lithium batteries can be remarkably improved, but dendritic crystal growth and volume expansion in the charging and discharging processes of lithium metal batteries cause poor battery cycle performance, and even cause safety problems.
Disclosure of Invention
The invention aims to optimize a positive electrode, a negative electrode and an electrolyte, firstly, a gradient core-shell nanowire composite positive electrode is prepared by a simple hydrothermal process, in the unique gradient positive electrode, the viscosity and the volume of a polymer dispersion liquid are controlled, so that a gradient core-shell nanowire positive electrode film has two different functional interfaces, meanwhile, the effective infiltration of the polymer electrolyte improves the interface problem in a positive electrode material, namely, the concentration of the polymer solution is accurately controlled to adjust the positive electrode/SSE, the interface of the positive electrode/current collector and the internal structure of the positive electrode, and the obtained gradient structure with two different fractal surfaces can provide smooth contact between the positive electrode/solid electrolyte interface and rapid electron transmission serving as the current collector, and in addition, the core-shell structure with a large-area contact interface of the internal structure of the positive electrode and stable structural strength can obviously increase the follow-up cycle The problems of complex reaction generated on a negative electrode interface, growth of lithium dendrite and volume expansion can be avoided by adopting a solid electrolyte method, and in the latter, a copper-nickel double metal layer is added into a negative electrode to guide lithium ion deposition and promote stable circulation of a lithium metal negative electrode.
In order to solve the problems of poor environment-friendly performance and low structural strength, the invention provides the following technical scheme: the high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery comprises the following steps of:
step one, preparing a battery anode material, adding a hydrogen peroxide solution into vanadium pentoxide, violently stirring the mixture to obtain a vanadium sol, respectively adding ionized water and polyethylene glycol into the obtained vanadium sol, simultaneously, carrying out ultrasonic treatment on a graphene oxide solution for 6 hours, mixing the well-dispersed GO solution with the vanadium sol, transferring the mixed solution into a high-pressure kettle, carrying out hydrothermal treatment in an oven, washing the product for three times until the waste liquid is clear and transparent, drying to obtain H2V3O 8/graphene nanowires, then preparing an H2V3O8 nanowire/graphene composite film, weighing the H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in the deionized water by strong ultrasonic treatment, then carrying out rapid suction filtration to form a film, drying in a ventilation oven, preparing electrolyte slurry by using the same method as the method for preparing the composite solid electrolyte, then carefully dropwise adding the electrolyte slurry on the prepared H2V3O8 nanowire/graphene composite film to ensure that the electrolyte is completely dropwise added in the range of the film and cannot permeate from the side surface to the bottom, drying the poured composite anode material in a vacuum oven, and taking out the composite anode material after the organic solvent is completely removed and putting the composite anode material into a glove box for later use;
step two, preparing a solid electrolyte, and preparing a PEO/LLZTO composite solid electrolyte by a traditional solution casting method, wherein firstly, PEO, LiTFSI and LLZTO are sequentially added into anhydrous acetonitrile, then the mixture is stirred by magnetic force to obtain uniform electrolyte slurry, and the slurry is poured on a polytetrafluoroethylene mould and further dried in a vacuum oven;
preparing a battery cathode, and preparing a lithium-philic copper-nickel bimetallic three-dimensional framework by a three-electrode electroplating method, wherein 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 are added into water to prepare a mixed solution, the mixed solution is used as an electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, foamed nickel is used as a working electrode, an electrochemical workstation is used for electroplating, the voltage and time set in the electroplating process are respectively 0.75V and 400s, the copper-nickel bimetallic material obtained by washing with ethanol and deionized water is sequentially dried in a vacuum drying box, and the copper-nickel bimetallic framework material can be obtained after punching;
step four, assembling the battery, firstly preparing the gradient core-shell nanowire anode into an electrode plate, taking the nanowire/graphene composite material, acetylene black and PVDF into a mortar, dropwise adding a small amount of NMP solvent, fully grinding into uniform slurry, then uniformly scraping and coating onto an aluminum foil current collector, drying, then punching into a round piece with the diameter by using a punching machine, drying for later use, wherein the anode plate has two different surfaces, the polymer-enriched side faces the electrolyte to enhance interface contact during assembling, the other side faces the electrode shell, steel meshes are supplemented to fill gaps in the battery as required, lithium metal is required to be deposited in a copper-nickel bimetallic framework material before assembling, copper-nickel bimetallic is taken as the anode, the lithium plate is taken as the cathode, constant-current discharge is carried out at the current density to form a composite lithium metal cathode, and the electrolyte is selected from PEO/LLZTO composite solid electrolyte during lithium battery assembling, the cathode adopts Li @ Cu-Ni, materials are sequentially placed in the order of a cathode shell, a cathode plate, a diaphragm, a composite lithium metal cathode and a cathode shell, electrolyte is dripped on an electrode plate/diaphragm interface to ensure full wetting, then a sealing machine is used for pressing the electrode plate/diaphragm interface into a complete battery, and the battery is kept stand to be tested after the surface is cleaned.
Further, the method comprises the following steps: according to the operation procedure in the first step, 10mL of 30% hydrogen peroxide solution (H2O2) is added to 0.237g of vanadium pentoxide (V2O5), and the mixture is stirred vigorously to obtain a vanadium sol.
Further, the method comprises the following steps: according to the operation steps in the first step, 50mL of deionized water (DI) and 0.04g of polyethylene glycol (PEG-4000) are respectively added to the obtained vanadium sol, and simultaneously, 2mL of Graphene Oxide (GO) solution (obtained by Hummers method) is dispersed by 30mL of deionized water, and after 6 hours of ultrasonic treatment, the well-dispersed GO solution is mixed with the vanadium sol.
Further, the method comprises the following steps: according to the operation steps in the first step, the mixed solution is transferred to a 100mL autoclave and is hydrothermal for 2 days in an oven at 180 ℃, the product is washed three times by water and ethanol alternately until the waste liquid is clear and transparent, and then the waste liquid is dried in air at 70 ℃ for 12 hours to obtain H2V3O 8/graphene nanowires.
Further, the method comprises the following steps: according to the operation steps in the first step, preparing the H2V3O8 nanowire/graphene composite film, weighing 30mg of H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in deionized water without additional additives, performing strong ultrasonic treatment for 30min to uniformly disperse the nanowire/graphene composite material, wherein the solution is uniform dark green and has no obvious particles, performing rapid suction filtration to form a film, drying the film in a ventilation oven at 70 ℃ for 24H, wherein the surface of the dried film is smooth and has no obvious particles, the film is soft and can be bent randomly, the thickness is about 30 mu m, preparing electrolyte slurry (EO: Li < + > 10: 1 mol%) by using the same method as the method for preparing the composite solid electrolyte, then carefully dropwise adding the electrolyte slurry on the prepared H2V3O8 nanowire/graphene composite film to ensure that the electrolyte is completely dropwise added in the range of the film and cannot permeate from the side surface to the bottom, drying the poured composite anode material in a vacuum oven at 60 ℃ for 24H, and taking out the mixture after the organic solvent is completely removed and putting the mixture into a glove box for later use.
Further, the method comprises the following steps: according to the procedure of step two, the conventional solution casting method for preparing PEO/LLZTO composite solid electrolyte, first, PEO (Mv 106g mol-1, Sigma Aldrich), litfsi (adin) and LLZTO (hefei kejing) are sequentially added to 20mL of anhydrous acetonitrile, wherein the molar ratio of EO to Li + is 8: 1, LLZTO in 15% of the total amount, then the mixture was mixed by magnetic stirring for 24 hours to obtain a homogeneous electrolyte slurry, which was poured on a teflon mold and further dried in a vacuum oven at 60 ℃ for 24 hours, all in a glove box filled with argon, with H2O and O2 contents below 0.1 ppm.
Further, the method comprises the following steps: according to the operation steps in the third step, the three-dimensional framework of the lithium-philic copper-nickel bimetal is prepared by the three-electrode electroplating method, and firstly, 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 are added into 50mL of water to prepare a mixed solution.
Further, the method comprises the following steps: according to the operation steps in the third step, the mixed solution is used as electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, 2 x 2cm2 foamed nickel is used as a working electrode, an electrochemical workstation is used for electroplating, the voltage and the time set in the electroplating process are respectively 0.75V and 400s, the copper-nickel bimetallic material obtained by washing with ethanol and deionized water is sequentially used, the drying is carried out in a vacuum drying box at the temperature of 60 ℃ for 3h, and the copper-nickel bimetallic negative electrode framework material can be obtained after punching.
Further, the method comprises the following steps: according to the operation steps in the fourth step, 35mg of the nanowire/graphene composite material, 15mg of acetylene black and 5mg of PVDF are placed in a mortar, a small amount of NMP solvent is dripped, the mixture is fully ground into uniform slurry, the uniform slurry is then evenly spread on an aluminum foil current collector, the aluminum foil current collector is dried at 70 ℃ overnight, then a sheet punching machine is used for punching a wafer with the diameter of 1cm, the wafer is dried for standby use, the positive plate has two different surfaces, the polymer enrichment side faces to electrolyte during assembly so as to enhance interface contact, the other side faces to an electrode shell, a steel mesh is supplemented as required to fill gaps in the battery, and all parts are ensured to be in close contact all the time.
Further, the method comprises the following steps: according to the operation steps in the fourth step, lithium metal is required to be deposited in the copper-nickel bimetal framework material before assembly, the copper-nickel bimetal is used as a positive electrode, a lithium sheet is used as a negative electrode, constant current discharge is carried out at the current density of 0.5mA/cm2 to form a composite lithium metal negative electrode (Li @ Cu-Ni), PEO/LLZTO composite solid electrolyte is selected as the electrolyte when the lithium battery is assembled, the Li @ Cu-Ni is adopted as the negative electrode, the materials are sequentially placed in the order of a positive electrode shell, a positive electrode sheet, a diaphragm, the composite lithium metal negative electrode and a negative electrode shell, 2-3 drops of electrolyte are dripped on an electrode sheet/diaphragm interface to ensure sufficient wetting, then a sealing machine is used for pressing to form a complete battery, and the complete battery is kept stand to be tested after the surface is cleaned.
The invention provides a high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery, which has the following beneficial effects: the cathode, the anode and the electrolyte are optimized, firstly, a gradient core-shell nanowire composite cathode is prepared by a simple hydrothermal process, in the unique gradient cathode, the viscosity and the volume of a polymer dispersion liquid are controlled, so that a gradient core-shell nanowire cathode film has two different functional interfaces, meanwhile, the effective infiltration of the polymer electrolyte improves the interface problem in a cathode material, namely, the cathode/SSE, the interface of the cathode/current collector and the internal structure of the cathode are adjusted by accurately controlling the concentration of the polymer solution, the obtained gradient structure with two different fractal surfaces can provide smooth contact between the cathode/solid electrolyte interfaces and rapid electron transmission serving as the current collector, and in addition, the core-shell structure with the large-area contact interface of the internal structure of the cathode and stable structural strength can obviously increase the ion/electron transmission during circulation The volume change of the input buffer solution and the buffer solution, effective interface engineering enables SSLB to have lower interface resistance, high capacity and good cycling stability, for the problems of complex reaction of a negative electrode interface, growth and volume expansion of lithium dendrite, the former can be avoided by adopting a solid electrolyte method, and the latter can guide lithium ion deposition and promote the stable cycle of a lithium metal negative electrode by adding a copper-nickel double metal layer modified three-dimensional framework material to the negative electrode and constructing a lithium-philic copper-nickel double metal layer on the lithium-phobic three-dimensional framework by adopting a three-electrode electroplating method.
Drawings
FIG. 1 is a schematic diagram of a specific process of a high performance heat-resistant gradient nanowire positive-grade and lithium-philic negative composite solid-state lithium battery according to the present invention;
FIG. 2 is a diagram of the structure and morphology of the solid electrolyte of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention;
FIG. 3 is a thermogravimetric plot of the composite solid electrolyte in an air atmosphere of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention;
FIG. 4 is a linear sweep voltammetry test chart of the composite electrolyte of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention;
FIG. 5 is a constant current lithium desorption test chart of a composite solid electrolyte lithium symmetric battery of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the invention at 0.1mA cm-2;
fig. 6 is an SEM image of the positive electrode/SSE interface before cycling of the high performance thermal gradient nanowire positive and lithium-philic negative composite solid state lithium battery of the present invention: a) gradient nanowire positive electrode, b) homogeneous nanowire positive electrode, and after cycling: c) gradient nanowire anodes, d) homogeneous nanowire anode schematic;
FIG. 7 is EIS curves of composite electrolytes of high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium batteries at different temperatures according to the present invention;
FIG. 8 is a schematic diagram of the transmission characteristics of the anode surfaces of different gradient nanowires of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention;
FIG. 9 is a schematic diagram of GIXRD diffraction, SEM morphology and EDS mapping of Cu-Ni composition of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention;
fig. 10 is a graph of (a) GITT curve and (b) diffusion coefficient versus discharge fraction of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid-state lithium battery of the present invention, and EIS plots of the gradient nanowire positive electrode and the homogeneous nanowire positive electrode SSLB: (c) pre-cycle, (d)100 post-cycle schematic;
fig. 11 is a graph of (a) GITT curve and (b) diffusion coefficient versus discharge fraction of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid-state lithium battery of the present invention, and EIS plots of the gradient nanowire positive electrode and the homogeneous nanowire positive electrode SSLB: (c) pre-cycle, (d)100 post-cycle schematic;
FIG. 12 is a graph of (a) a constant current charge and discharge curve at a current density of 1mA cm-2 and a cycle capacity of 1mA h cm-2 for a symmetric battery composed of Li @ Cu-Ni, Li @ NF and Li @ CF electrodes, (b) an amplified charge and discharge curve for 5-20 hours, (c) a constant current charge and discharge curve at a current density of 10mA cm-2 and a cycle capacity of 1mA h cm-2 for a symmetric battery composed of Li @ Cu-Ni, Li @ NF and Li @ CF electrodes, and (d) an amplified charge and discharge curve for 2-8 hours, for a high performance, heat-resistant gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery of the present invention;
FIG. 13 is a graphical representation of different lithium deposition amounts of the high performance heat-resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention, wherein (a-c) Cu-Ni, (d-f) CF and (g-i) NF correspond to SEM images of different lithium deposition amounts, and the SEM images of (a, d and g)1mA h cm-2, (b, e and h)2mA h cm-2 and (c, f and i)3mA h cm-2;
FIG. 14 is a schematic diagram of a) cycle performance of SSE at a current density of 100mA g-1 at room temperature, and (b) a charge-discharge curve after 100 cycles of cycle, in the high-performance heat-resistant gradient nanowire positive-and lithium-philic negative-electrode composite solid-state lithium battery of the present invention;
FIG. 15 is a graph of the charge/discharge curves of (a) a gradient nanowire positive electrode and (b) a homogeneous nanowire positive electrode at a current density of 50mA g-1 to 300mA g-1, (c) a rate performance graph at a current density of 50mA g-1 to 300mA g-1 based on SSE, for a high performance, heat resistant gradient nanowire positive and lithium-philic negative composite solid state lithium battery of the present invention;
fig. 16 is SEM images of the cross section and surface of the gradient nanowire positive electrode of the high performance heat resistant gradient nanowire positive and lithium-philic negative composite solid lithium battery of the present invention.
Detailed Description
Referring to fig. 1-16, the present invention provides a technical solution: the high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery comprises the following steps of:
step one, preparing a battery anode material, adding a hydrogen peroxide solution into vanadium pentoxide, violently stirring the mixture to obtain a vanadium sol, respectively adding ionized water and polyethylene glycol into the obtained vanadium sol, simultaneously, carrying out ultrasonic treatment on a graphene oxide solution for 6 hours, mixing the well-dispersed GO solution with the vanadium sol, transferring the mixed solution into a high-pressure kettle, carrying out hydrothermal treatment in an oven, washing the product for three times until the waste liquid is clear and transparent, drying to obtain H2V3O 8/graphene nanowires, then preparing an H2V3O8 nanowire/graphene composite film, weighing the H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in the deionized water by strong ultrasonic treatment, then carrying out rapid suction filtration to form a film, drying in a ventilation oven, preparing electrolyte slurry by using the same method as the method for preparing the composite solid electrolyte, then carefully dropwise adding the electrolyte slurry on the prepared H2V3O8 nanowire/graphene composite film to ensure that the electrolyte is completely dropwise added in the range of the film and cannot permeate from the side surface to the bottom, drying the poured composite anode material in a vacuum oven, and taking out the composite anode material after the organic solvent is completely removed and putting the composite anode material into a glove box for later use;
step two, preparing a solid electrolyte, and preparing a PEO/LLZTO composite solid electrolyte by a traditional solution casting method, wherein firstly, PEO, LiTFSI and LLZTO are sequentially added into anhydrous acetonitrile, then the mixture is stirred by magnetic force to obtain uniform electrolyte slurry, and the slurry is poured on a polytetrafluoroethylene mould and further dried in a vacuum oven;
preparing a battery cathode, and preparing a lithium-philic copper-nickel bimetallic three-dimensional framework by a three-electrode electroplating method, wherein 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 are added into water to prepare a mixed solution, the mixed solution is used as an electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, foamed nickel is used as a working electrode, an electrochemical workstation is used for electroplating, the voltage and time set in the electroplating process are respectively 0.75V and 400s, the copper-nickel bimetallic material obtained by washing with ethanol and deionized water is sequentially dried in a vacuum drying box, and the copper-nickel bimetallic framework material can be obtained after punching;
step four, assembling the battery, firstly preparing the gradient core-shell nanowire anode into an electrode plate, taking the nanowire/graphene composite material, acetylene black and PVDF into a mortar, dropwise adding a small amount of NMP solvent, fully grinding into uniform slurry, then uniformly scraping and coating onto an aluminum foil current collector, drying, then punching into a round piece with the diameter by using a punching machine, drying for later use, wherein the anode plate has two different surfaces, the polymer-enriched side faces the electrolyte to enhance interface contact during assembling, the other side faces the electrode shell, steel meshes are supplemented to fill gaps in the battery as required, lithium metal is required to be deposited in a copper-nickel bimetallic framework material before assembling, copper-nickel bimetallic is taken as the anode, the lithium plate is taken as the cathode, constant-current discharge is carried out at the current density to form a composite lithium metal cathode, and the electrolyte is selected from PEO/LLZTO composite solid electrolyte during lithium battery assembling, the cathode adopts Li @ Cu-Ni, materials are sequentially placed in the order of a cathode shell, a cathode plate, a diaphragm, a composite lithium metal cathode and a cathode shell, electrolyte is dripped on an electrode plate/diaphragm interface to ensure full wetting, then a sealing machine is used for pressing the electrode plate/diaphragm interface into a complete battery, and the battery is kept stand to be tested after the surface is cleaned.
Specifically, the method comprises the following steps: according to the procedure in the first step, 10mL of 30% hydrogen peroxide solution (H2O2) was added to 0.237g of vanadium pentoxide (V2O5), and the mixture was vigorously stirred to obtain a vanadium sol.
Specifically, the method comprises the following steps: according to the operation steps in the first step, 50mL of deionized water (DI) and 0.04g of polyethylene glycol (PEG-4000) are respectively added to the obtained vanadium sol, meanwhile, 2mL of Graphene Oxide (GO) solution (obtained by a Hummers method) is dispersed by 30mL of deionized water, and after 6 hours of ultrasonic treatment, the well-dispersed GO solution is mixed with the vanadium sol.
Specifically, the method comprises the following steps: according to the operation procedure in the first step, the mixed solution is transferred to a 100mL autoclave and is hydrothermal for 2 days in an oven at 180 ℃, the product is washed three times by water and ethanol alternately until the waste liquid is clear and transparent, and then is dried in air at 70 ℃ for 12H to obtain H2V3O 8/graphene nanowires.
Specifically, the method comprises the following steps: preparing an H2V3O8 nanowire/graphene composite film according to the operation steps in the first step, weighing 30mg of the H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in deionized water without an additional additive, performing strong ultrasonic treatment for 30min to uniformly disperse the nanowire/graphene composite material, wherein the solution is uniform dark green and has no obvious particles, performing rapid suction filtration to form a film, drying the film in a ventilating oven at 70 ℃ for 24H, wherein the dried film has a smooth surface and no obvious particles, is soft and can be bent randomly, and has a thickness of about 30 mu m, preparing an electrolyte slurry (EO: Li +: 10: 1 mol%) by using the same method as the preparation of the composite solid electrolyte, then carefully dropwise adding the electrolyte slurry on the prepared H2V3O8 nanowire/graphene composite film to ensure that the electrolyte is completely dropwise added in the range of the film and cannot permeate from the side surface to the bottom, drying the poured composite anode material in a vacuum oven at 60 ℃ for 24 hours, and taking out the mixture after the organic solvent is completely removed and putting the mixture into a glove box for later use.
Specifically, the method comprises the following steps: according to the procedure of step two, a PEO/LLZTO composite solid electrolyte is prepared by a conventional solution casting method, first, PEO (Mv 106g mol-1, Sigma Aldri ch), litfsi (adin), and LLZTO (hefei kejing) are sequentially added to 20mL of anhydrous acetonitrile, wherein the molar ratio of EO to Li + is 8: 1, LLZTO in 15% of the total amount, then the mixture was mixed by magnetic stirring for 24 hours to obtain a homogeneous electrolyte slurry, which was poured on a teflon mold and further dried in a vacuum oven at 60 ℃ for 24 hours, all in a glove box filled with argon, with H2O and O2 contents below 0.1 ppm.
Specifically, the method comprises the following steps: according to the operation steps in the third step, a three-dimensional framework of a lithium-philic copper-nickel bimetal was prepared by a three-electrode plating method, and first, 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 were added to 50mL of water to prepare a mixed solution.
Specifically, the method comprises the following steps: according to the operation steps in the third step, the mixed solution is used as electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, 2 x 2cm2 foamed nickel is used as a working electrode, an electrochemical workstation is used for electroplating, the voltage and the time set in the electroplating process are respectively 0.75V and 400s, the obtained copper-nickel bimetallic material is sequentially washed by ethanol and deionized water, the copper-nickel bimetallic material is dried in a vacuum drying box at the temperature of 60 ℃ for 3h, and then the copper-nickel bimetallic negative electrode framework material can be obtained after punching.
Specifically, the method comprises the following steps: according to the operation steps in the fourth step, 35mg of the nanowire/graphene composite material, 15mg of acetylene black and 5mg of PVDF are placed in a mortar, a small amount of NMP solvent is dripped, the mixture is fully ground into uniform slurry, the uniform slurry is then evenly spread on an aluminum foil current collector, the aluminum foil current collector is dried at 70 ℃ overnight, then a sheet punching machine is used for punching a wafer with the diameter of 1cm, the wafer is dried for standby use, the positive plate has two different surfaces, the polymer enrichment side faces the electrolyte during assembly so as to enhance interface contact, the other side faces an electrode shell, a steel mesh is supplemented as required to fill gaps in the battery, and all parts are ensured to be in close contact all the time.
Specifically, the method comprises the following steps: according to the operation steps in the fourth step, lithium metal is required to be deposited in a copper-nickel bimetal framework material before assembly, a copper-nickel bimetal is taken as an anode, a lithium sheet is taken as a cathode, constant current discharge is carried out at the current density of 0.5mA/cm2 to form a composite lithium metal cathode (Li @ Cu-Ni), PEO/LLZTO composite solid electrolyte is selected as the electrolyte when the lithium battery is assembled, Li @ Cu-Ni is adopted as the cathode, materials are sequentially placed in the order of an anode shell, the anode sheet, a diaphragm, the composite lithium metal cathode and a cathode shell, 2-3 drops of electrolyte are dripped on an electrode plate/diaphragm interface to ensure sufficient wetting, then a sealing machine is used for pressing to form a complete battery, and the complete battery is kept stand to be tested after the surface is cleaned.
The method of the examples was performed for detection analysis and compared to the prior art to yield the following data:
| stimulating the effects of consumption | Operation guide effect | |
| Examples | Is higher than | Is higher than |
| Prior Art | Is lower than | Is lower than |
According to the table data, when the embodiment is used, the consumption frequency is further increased through the block consensus method based on comprehensive circulation conversion, and the business incubation management guidance effect of the merchant is improved.
The invention provides a high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery, which comprises the following steps: step one, preparing a battery anode material, adding a hydrogen peroxide solution into vanadium pentoxide, violently stirring the mixture to obtain a vanadium sol, respectively adding ionized water and polyethylene glycol into the obtained vanadium sol, simultaneously, carrying out ultrasonic treatment on a graphene oxide solution for 6 hours, mixing the well-dispersed GO solution with the vanadium sol, transferring the mixed solution into a high-pressure kettle, carrying out hydrothermal treatment in an oven, washing the product for three times until the waste liquid is clear and transparent, drying to obtain H2V3O 8/graphene nanowires, then preparing an H2V3O8 nanowire/graphene composite film, weighing the H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in the deionized water by strong ultrasonic treatment, then carrying out rapid suction filtration to form a film, drying in a ventilation oven, preparing electrolyte slurry by using the same method as the method for preparing the composite solid electrolyte, then carefully dripping electrolyte slurry on the prepared H2V3O8 nanowire/graphene composite film to ensure that the electrolyte is completely dripped in the range of the film and does not permeate from the side surface to the bottom, drying the poured composite cathode material in a vacuum oven, taking out the composite cathode material after an organic solvent is completely removed, putting the composite cathode material into a glove box for standby, adding 10mL of 30% hydrogen peroxide solution (H2O2) into 0.237g of vanadium pentoxide (V2O5), violently stirring the mixture to obtain vanadium sol, respectively adding 50mL of deionized water (DI) and 0.04g of polyethylene glycol (PEG-4000) into the obtained vanadium sol, simultaneously dispersing 2mL of Graphene Oxide (GO) solution (obtained by a Hummers method) by using 30mL of deionized water, mixing the well dispersed GO solution with the vanadium sol after 6 hours of ultrasonic treatment, respectively adding 50mL of deionized water (DI) and 0.04g of polyethylene glycol (PEG-4000) into the obtained vanadium sol, meanwhile, dispersing 2mL of Graphene Oxide (GO) solution (obtained by a Hummers method) by 30mL of deionized water, after 6 hours of ultrasonic treatment, mixing the well-dispersed GO solution with vanadium sol to prepare an H2V3O8 nanowire/graphene composite film, weighing 30mg of H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in the deionized water without additional additives, performing strong ultrasonic treatment for 30 minutes to uniformly disperse the nanowire/graphene composite material, wherein the solution is uniform dark green and has no obvious particles, performing rapid suction filtration to form a film, drying the film for 24 hours in a ventilation oven at 70 ℃, flattening the surface of the dried film, having no obvious particles, being soft and capable of being bent at will and having a thickness of about 30 mu m, preparing electrolyte slurry (EO: Li +: 10: 1 mol%) by the same method as the preparation of the composite solid electrolyte, then dripping the electrolyte slurry on the well-prepared H2V3O8 nanowire/graphene composite film carefully, ensuring that the electrolyte is completely dripped in the range of the film and cannot permeate to the bottom from the side surface, drying the poured composite anode material in a vacuum oven at 60 ℃ for 24 hours, taking out the mixture after the organic solvent is completely removed and putting the mixture into a glove box for standby, preparing the PEO/LLZTO composite solid electrolyte through a traditional solution casting method, firstly, sequentially adding the PEO, the LiTFSI and the LLZTO into anhydrous acetonitrile, the mixture was then stirred magnetically to obtain a homogeneous electrolyte slurry, which was poured onto a teflon mold and further dried in a vacuum oven, a conventional solution casting method to prepare PEO/LLZTO composite solid electrolyte, first PEO (Mv 106g mol-1, Sigma Aldrich), litfsi (aladdin) and LLZTO (hefei kejing) were added sequentially to 20mL anhydrous acetonitrile, wherein the molar ratio of EO and Li + was 8: 1, LLZTO accounts for 15 percent of the total amount, then the mixture is mixed for 24 hours by magnetic stirring to obtain uniform electrolyte slurry, the slurry is poured on a polytetrafluoroethylene mould and is further dried for 24 hours in a vacuum oven at 60 ℃, all the processes are carried out in a glove box filled with argon, the content of H2O and O2 is less than 0.1ppm, step three, the preparation of the battery cathode and the preparation of the copper-nickel bimetal three-dimensional framework with lithium affinity by a three-electrode electroplating method are carried out, firstly, 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 are added into water to prepare a mixed solution, then the mixed solution is used as an electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, an electrochemical workstation is used for electroplating, the voltage and the time set in the electroplating process are respectively 0.75V and 400s, and the obtained copper-nickel bimetal material is sequentially washed by ethanol and deionized water, drying in a vacuum drying oven, punching to obtain a copper-nickel bimetallic negative electrode framework material, preparing a copper-nickel bimetallic three-dimensional framework with lithium affinity by a three-electrode electroplating method, firstly, adding 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 into 50mL of water to prepare a mixed solution, taking the mixed solution as an electroplating solution, taking Pt as a counter electrode, taking a calomel electrode as an indicating electrode and 2 x 2cm2 foamed nickel as a working electrode, electroplating by using an electrochemical workstation, washing the copper-nickel bimetallic material obtained by the electroplating process with ethanol and deionized water in sequence, drying for 3 hours in the vacuum drying oven at 60 ℃, punching to obtain the copper-nickel bimetallic negative electrode framework material, assembling the battery, preparing a gradient core-shell nanowire positive electrode into an electrode plate, putting a nanowire/graphene composite material, acetylene black and PVDF (polyvinylidene fluoride) into a mortar, dropwise adding a small amount of NMP (N-methyl pyrrolidone) solvent, fully grinding into uniform slurry, uniformly scraping and coating the slurry on an aluminum foil current collector, drying, punching into a round piece with a diameter by using a punching machine, drying for later use, wherein a positive plate has two different surfaces, the polymer-enriched side faces to electrolyte during assembly to enhance interface contact, the other side faces to an electrode shell, a steel mesh is supplemented as required to fill gaps in a battery, lithium metal is required to be deposited in a copper-nickel bimetallic framework material before assembly, a copper-nickel bimetallic is used as a positive electrode, a lithium plate is used as a negative electrode, constant current discharge is carried out at the current density to form a composite lithium metal negative electrode, the electrolyte during lithium battery assembly is prepared from PEO/LLZTO composite solid electrolyte, the negative electrode is prepared from Li @ Cu-Ni, and the positive electrode shell, the positive plate, a diaphragm and the composite lithium metal negative electrode, Placing materials in sequence of a negative electrode shell, dropwise adding electrolyte on an electrode plate/diaphragm interface to ensure sufficient wetting, pressing the materials into a complete battery by using a sealing machine, cleaning the surface, standing the battery to be tested, taking 35mg of nanowire/graphene composite material, 15mg of acetylene black and 5mg of PVDF, putting a small amount of NMP solvent into a mortar, fully grinding the mixture into uniform slurry, uniformly scraping the slurry onto an aluminum foil current collector, drying the aluminum foil current collector for one night at 70 ℃, then punching the slurry into a wafer with the diameter of 1cm by using a punching machine, drying the wafer for later use, wherein the positive plate has two different surfaces, during assembly, a polymer-enriched side faces the electrolyte to enhance interface contact, the other side faces the electrode shell, supplementing a steel mesh according to needs to fill gaps in the battery, ensuring that all parts are always in close contact, depositing lithium metal in a copper-nickel bimetallic framework material before assembly, taking a copper-nickel bimetallic material as a positive electrode, and preparing a lithium battery, The lithium sheet is used as a negative electrode, constant current discharge is carried out under the current density of 0.5mA/cm2 to form a composite lithium metal negative electrode (Li @ Cu-Ni), PEO/LLZTO composite solid electrolyte is selected as the electrolyte when the lithium battery is assembled, Li @ Cu-Ni is adopted as the negative electrode, materials are sequentially placed in the order of a positive electrode shell, the positive electrode sheet, a diaphragm, the composite lithium metal negative electrode and a negative electrode shell, 2-3 drops of electrolyte are dripped on an electrode sheet/diaphragm interface to ensure full wetting, then a sealing machine is used for pressing the materials into a complete battery, and the complete battery is kept stand to be tested after the surface is cleaned.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The high-performance heat-resistant gradient nanowire positive-grade and lithium-philic negative electrode composite solid-state lithium battery is characterized by comprising the following steps of:
step one, preparing a battery anode material, adding a hydrogen peroxide solution into vanadium pentoxide, violently stirring the mixture to obtain a vanadium sol, respectively adding ionized water and polyethylene glycol into the obtained vanadium sol, simultaneously, carrying out ultrasonic treatment on a graphene oxide solution for 6 hours, mixing the well-dispersed GO solution with the vanadium sol, transferring the mixed solution into a high-pressure kettle, carrying out hydrothermal treatment in an oven, washing the product for three times until the waste liquid is clear and transparent, drying to obtain H2V3O 8/graphene nanowires, then preparing an H2V3O8 nanowire/graphene composite film, weighing the H2V3O8 nanowire/graphene composite material, dispersing the nanowire/graphene composite material in the deionized water by strong ultrasonic treatment, then carrying out rapid suction filtration to form a film, drying in a ventilation oven, preparing electrolyte slurry by using the same method as the method for preparing the composite solid electrolyte, then carefully dropwise adding the electrolyte slurry on the prepared H2V3O8 nanowire/graphene composite film to ensure that the electrolyte is completely dropwise added in the range of the film and cannot permeate from the side surface to the bottom, drying the poured composite anode material in a vacuum oven, and taking out the composite anode material after the organic solvent is completely removed and putting the composite anode material into a glove box for later use;
step two, preparing a solid electrolyte, and preparing a PEO/LLZTO composite solid electrolyte by a traditional solution casting method, wherein firstly, PEO, LiTFSI and LLZTO are sequentially added into anhydrous acetonitrile, then the mixture is stirred by magnetic force to obtain uniform electrolyte slurry, and the slurry is poured on a polytetrafluoroethylene mould and further dried in a vacuum oven;
preparing a battery cathode, and preparing a lithium-philic copper-nickel bimetallic three-dimensional framework by a three-electrode electroplating method, wherein 13.1415g of NiSO4, 1.545g H3BO3 and 0.399025g of CuSO4 are added into water to prepare a mixed solution, the mixed solution is used as an electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, foamed nickel is used as a working electrode, an electrochemical workstation is used for electroplating, the voltage and time set in the electroplating process are respectively 0.75V and 400s, the copper-nickel bimetallic material obtained by washing with ethanol and deionized water is sequentially dried in a vacuum drying box, and the copper-nickel bimetallic framework material can be obtained after punching;
step four, assembling the battery, firstly preparing the gradient core-shell nanowire anode into an electrode plate, taking the nanowire/graphene composite material, acetylene black and PVDF into a mortar, dropwise adding a small amount of NMP solvent, fully grinding into uniform slurry, then uniformly scraping and coating onto an aluminum foil current collector, drying, then punching into a round piece with the diameter by using a punching machine, drying for later use, wherein the anode plate has two different surfaces, the polymer-enriched side faces the electrolyte to enhance interface contact during assembling, the other side faces the electrode shell, steel meshes are supplemented to fill gaps in the battery as required, lithium metal is required to be deposited in a copper-nickel bimetallic framework material before assembling, copper-nickel bimetallic is taken as the anode, the lithium plate is taken as the cathode, constant-current discharge is carried out at the current density to form a composite lithium metal cathode, and the electrolyte is selected from PEO/LLZTO composite solid electrolyte during lithium battery assembling, the cathode adopts Li @ Cu-Ni, materials are sequentially placed in the order of a cathode shell, a cathode plate, a diaphragm, a composite lithium metal cathode and a cathode shell, electrolyte is dripped on an electrode plate/diaphragm interface to ensure full wetting, then a sealing machine is used for pressing the electrode plate/diaphragm interface into a complete battery, and the battery is kept stand to be tested after the surface is cleaned.
2. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the procedure in step one, 10mL of 30% hydrogen peroxide solution (H)2O2) To 0.237g of vanadium pentoxide (V)2O5) And the mixture was vigorously stirred to obtain a vanadium sol.
3. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the operation steps in the first step, 50mL of deionized water (DI) and 0.04g of polyethylene glycol (PEG-4000) are respectively added to the obtained vanadium sol, and simultaneously, 2mL of Graphene Oxide (GO) solution (obtained by Hummers method) is dispersed by 30mL of deionized water, and after 6 hours of ultrasonic treatment, the well-dispersed GO solution is mixed with the vanadium sol.
4. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the procedure in step one, the mixed solution was transferred to a 100mL autoclave and hydrothermal 2 days in an oven at 180 ℃, the product was washed three times with water and ethanol alternately until the waste liquid was clear and transparent, and then dried in air at 70 ℃ for 12H to obtain H2V3O8Graphene nanowires.
5. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the operating procedure in step one, the preparation H2V3O8Weighing 30mg of H in the nanowire/graphene composite film2V3O8Dispersing the nanowire/graphene composite material in deionized water without additional additives, performing strong ultrasound for 30min to uniformly disperse the nanowire/graphene composite material, wherein the solution is uniformly dark green and has no obvious particles, performing rapid suction filtration to form a film, drying the film in a ventilation oven at 70 ℃ for 24H, flattening the surface of the dried film, having no obvious particles, being soft and freely bendable, and having a thickness of about 30 mu m, preparing electrolyte slurry (EO: Li + ═ 10: 1 mol%) by using the same method as the method for preparing the composite solid electrolyte, and carefully dropwise adding the electrolyte slurry into the prepared H2V3O8On the nanowire/graphene composite film, the electrolyte is ensured to be completely dripped in the film range and not to permeate to the bottom from the side surface, the poured composite anode material is dried in a vacuum oven at 60 ℃ for 24 hours, and the composite anode material is taken out and put into gloves after the organic solvent is completely removedAnd (5) reserving the box.
6. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the procedure of step two, the conventional solution casting method for preparing PEO/LLZTO composite solid electrolyte, first, PEO (Mv 106g mol-1, Sigma Aldrich), LiTFSI (Aladdin) and LLZTO (HEFEI KEJING) were sequentially added to 20mL of anhydrous acetonitrile, in which EO and Li were used+In a molar ratio of 8: LLZTO accounts for 15% of the total amount, then the mixture is mixed by magnetic stirring for 24 hours to obtain a homogeneous electrolyte slurry, the slurry is cast on a polytetrafluoroethylene mold and further dried in a vacuum oven at 60 ℃ for 24 hours, all processes should be carried out in a glove box filled with argon, H2O and O2The content is less than 0.1 ppm.
7. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the operation steps in the third step, the three-dimensional framework of the copper-nickel bimetal with lithium affinity is prepared by a three-electrode electroplating method, firstly, 13.1415g of NiSO4、1.545g H3BO3、0.399025g CuSO4The mixture was added to 50mL of water to prepare a mixed solution.
8. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the operation steps in the third step, the mixed solution is used as electroplating solution, Pt is used as a counter electrode, a calomel electrode is used as an indicating electrode, and the thickness of the mixed solution is 2 multiplied by 2cm2And (3) taking foamed nickel as a working electrode, electroplating by using an electrochemical workstation, sequentially washing the copper-nickel bimetallic material obtained by using ethanol and deionized water for 0.75V and 400s respectively in the electroplating process, drying the copper-nickel bimetallic material in a vacuum drying oven at 60 ℃ for 3h, and punching to obtain the copper-nickel bimetallic negative electrode framework material.
9. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the operation steps in the fourth step, 35mg of the nanowire/graphene composite material, 15mg of acetylene black and 5mg of PVDF are placed in a mortar, a small amount of NMP solvent is dripped, the mixture is fully ground into uniform slurry, the uniform slurry is then evenly spread on an aluminum foil current collector, the aluminum foil current collector is dried at 70 ℃ overnight, then a sheet punching machine is used for punching a wafer with the diameter of 1cm, the wafer is dried for standby use, the positive plate has two different surfaces, the polymer enrichment side faces to electrolyte during assembly so as to enhance interface contact, the other side faces to an electrode shell, a steel mesh is supplemented as required to fill gaps in the battery, and all parts are ensured to be in close contact all the time.
10. The high performance thermal gradient nanowire positive and lithium-philic negative electrode composite solid state lithium battery as claimed in claim 1, comprising the steps of: according to the operation steps in the fourth step, lithium metal is deposited in the copper-nickel bimetal framework material before assembly, the copper-nickel bimetal is used as a positive electrode, a lithium sheet is used as a negative electrode, and the concentration of the lithium metal is 0.5mA/cm2The current density of the composite lithium metal negative electrode is constant current discharge to form a composite lithium metal negative electrode (Li @ Cu-Ni), when the lithium battery is assembled, the electrolyte is PEO/LLZTO composite solid electrolyte, the negative electrode is Li @ Cu-Ni, materials are sequentially placed in the order of a positive electrode shell, a positive electrode plate, a diaphragm, the composite lithium metal negative electrode and a negative electrode shell, 2-3 drops of electrolyte are dripped on an electrode plate/diaphragm interface, sufficient wetting is guaranteed, then the complete battery is pressed by a sealing machine, and the complete battery is kept stand to be tested after the surface is cleaned.
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