CN114551977A - Elastic component, preparation method thereof and application of elastic component in all-solid-state battery - Google Patents

Elastic component, preparation method thereof and application of elastic component in all-solid-state battery Download PDF

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CN114551977A
CN114551977A CN202110969626.3A CN202110969626A CN114551977A CN 114551977 A CN114551977 A CN 114551977A CN 202110969626 A CN202110969626 A CN 202110969626A CN 114551977 A CN114551977 A CN 114551977A
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aluminum alloy
alloy sheet
sponge layer
flexible sponge
solution
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CN114551977B (en
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宫娇娇
陈军
黄建根
郑利峰
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Wanxiang A123 Systems Asia Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to the field of solid lithium ion batteries, and discloses an elastic component, a preparation method thereof and application thereof in all-solid batteries. According to the invention, the polymer material and the metal conductive material are integrated on the flexible sponge, and are compounded with the modified metal sheet to obtain the elastic component for the solid battery, the poor contact caused by the volume change of the positive and negative electrode materials in the charging and discharging process is effectively buffered through the flexible deformation capacity of the flexible base material, the metal sheet provides high mechanical support strength, the conductivity and the mechanical strength of the elastic component are simultaneously improved, and the electrochemical performance and the cycle life of the solid battery are obviously improved while an effective continuous electronic transmission path is ensured.

Description

Elastic component, preparation method thereof and application of elastic component in all-solid-state battery
Technical Field
The invention relates to the field of solid lithium ion batteries, in particular to an elastic component, a preparation method thereof and application thereof in all-solid batteries.
Background
Solid-state batteries using metallic lithium as the negative electrode can greatly improve energy density and safety compared to conventional lithium ion secondary batteries using liquid electrolytes, but various recent reports still show that growth of lithium dendrites at room temperature leads to failure of solid-state batteries. In addition, due to low compatibility of the solid/solid interface, the current density distribution is not uniform due to incomplete contact of the interface, and the formation and growth of lithium dendrites are easily caused by local over-high current density, thereby reducing the cycle life and safety of the solid battery. The effective contact area of the solid battery electrode and the solid electrolyte can be increased by applying reasonable external pressure, the internal resistance of the all-solid battery can be reduced, the uniformity of current distribution is increased, and the comprehensive performance of the battery is improved.
For example, an "all-solid battery and all-solid battery system" disclosed in chinese patent literature, having a publication number of CN112133924A, is disclosed as relating to an all-solid battery and an all-solid battery system. The main object of this publication is to provide an all-solid-state battery having high coulombic efficiency even when the thickness of the negative electrode active material layer varies due to charge and discharge. In this publication, the problem is solved by providing an all-solid battery specifically including: the negative electrode includes at least a negative electrode current collector having a current collecting portion and an elastic portion disposed on the opposite side of the solid dielectric layer with respect to the current collecting portion. According to the invention, the elastic part is added on the side of the negative electrode current collector, so that external pressure is applied in the charge and discharge process to inhibit the volume change of the negative electrode in the charge and discharge process, and the coulomb efficiency of the solid lithium battery is improved.
The elastic component in the prior art is made of metal materials or high polymer materials, and both the metal materials and the high polymer materials have the defects that the former has good conductivity but low elasticity, and the latter has high elasticity but low electronic conductivity, so that both the metal materials and the high polymer materials have certain technical limitations when being used independently.
In order to solve the above problems, an elastic member, a method for producing the same, and use in an all-solid battery are required.
Disclosure of Invention
The invention aims to overcome the problems that the elasticity is poor when a metal material is selected as an elastic component and the electronic conductivity is poor when a high polymer material is selected as the elastic component in the prior art, and provides an all-solid battery containing the elastic component and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an elastic component comprises a flexible sponge layer and an aluminum alloy sheet which are attached; the flexible sponge layer is loaded with polyaniline and metal filler particles, the surface of the aluminum alloy sheet is loaded with polyaniline and graphene, and the flexible sponge layer is bonded with the aluminum alloy sheet through conductive adhesive.
The elastic component is applied to the all-solid-state battery and consists of a flexible sponge layer loaded with polyaniline and metal filler particles and an aluminum alloy sheet loaded with graphene and polyaniline on the surface, so that the interface between a positive electrode and a negative electrode and a solid electrolyte is ensured to be always in close contact in the charging and discharging processes, the elastic component can effectively avoid the generation of a large number of microscopic gaps due to the volume change of the materials of the positive electrode and the negative electrode, the internal resistance and the polarization loss of the battery are increased, the flexible sponge layer provides a flexible matrix to buffer the volume change of the electrodes in the charging and discharging processes, and the aluminum alloy sheet provides high mechanical strength, so that the electrochemical performance and the cycle life of the solid-state battery are improved.
Preferably, the thickness of the flexible sponge layer is 0.5-5 mm, the porosity is 30-60%, and the flexible sponge layer can be one or more of polyurethane, nylon, polytetrafluoroethylene and polycarbonate; the flexible sponge layer with the thickness can provide good elasticity, and the size of the battery is not increased.
Preferably, the thickness of the aluminum alloy sheet is 0.5-5 mm, and the aluminum alloy sheet also comprises one or more elements of magnesium, manganese, iron, silicon, copper, chromium, nickel and zinc besides aluminum element; the aluminum alloy sheet with the thickness can provide a good mechanical supporting effect, the size of the battery is not increased, and the alloy contains various different metal elements, so that the improvement of the conductive effect of the metal sheet is facilitated.
The invention also provides a preparation method of the elastic component, which comprises the following steps:
A) mixing Mg (NO)3)2·6H2O and Al (NO)3)3·9H2Dispersing O in water, and then stirring the mixture by a strong machine until the O is completely dissolved to form a mixed metal solution A; dispersing sodium hydroxide and sodium carbonate in water to form an alkaline solution B;
B) dripping the alkaline solution B into the mixed metal solution A under the condition of continuous stirring, after the stirring is finished, preserving the temperature of the mixed solution at the temperature of 100-120 ℃ for 20-30 hours, cooling, washing, filtering, drying the obtained solid material at the temperature of 50-80 ℃, and finally calcining in the air for 4-7 hours to obtain metal filler particles;
C) adding the metal filler particles and aniline into water, performing ultrasonic dispersion at normal temperature to obtain a colloidal suspension, then adding hydrochloric acid into the colloidal suspension, then continuously adding ammonium persulfate into the mixed solution, and stirring for 30-60 minutes at 5-20 ℃ to obtain a solution C;
D) immersing the flexible sponge layer into the solution C, standing at 5-20 ℃, taking out the immersed flexible sponge layer, washing and drying to obtain the flexible sponge layer loaded with polyaniline and metal fillers;
E) sealing the side surface of the aluminum alloy sheet by using insulating resin, washing the upper surface and the lower surface of the aluminum alloy sheet by using dilute nitric acid, and then putting the aluminum alloy sheet into an electrolytic solution which is stirred in advance for 10-20h for electroplating to obtain the aluminum alloy sheet of which the surface is loaded with polyaniline and graphene;
F) and D), bonding the flexible sponge layer loaded with the polyaniline and the metal filler in the step D) and the aluminum alloy sheet loaded with the polyaniline and the graphene on the surface in the step E) by using a conductive adhesive to obtain the elastic component.
According to the invention, after the metal filler is subjected to ultrasonic treatment in an aniline solution to a uniformly dispersed colloidal suspension, ammonium persulfate is added for initiation, the metal filler is used as a filler and added into the polyaniline material, then, in the process of dipping the flexible sponge layer, the polyaniline material modified by the metal filler with low molecular weight is dipped into the internal pores of the flexible sponge layer, at the moment, the polymerization reaction is still carried out, the polyaniline dipped into the flexible sponge layer is polymerized continuously, finally, an interpenetrating cross-linked network structure of the polyaniline filled with the conductive metal filler is formed in the flexible sponge layer to form a conductive channel, the polyaniline and the metal filler have high electronic conductivity, the electronic conductivity of the flexible sponge layer can be improved, and the adverse effect of a low-conductivity elastic component on the performance of the solid battery is avoided; the metal filler is dispersed into the size of 1-100nm by ultrasonic, the specific surface area is larger, the conductivity of the flexible sponge layer is increased, and meanwhile, the mechanical property of the flexible sponge layer is greatly improved by the metal filler with the particle size.
The surface of the aluminum alloy sheet is coated with the high-conductivity polyaniline/graphene mixed layer, the polyaniline improves the distribution uniformity of graphene on the aluminum alloy sheet, enhances the adhesive force between the graphene and the conductive adhesive and the flexible sponge layer, improves the interface compatibility between the flexible sponge layer and the aluminum alloy sheet, the polyaniline on the surface can form a more uniform surface electric field, and meanwhile, the polyaniline and the graphene have excellent electronic conductivity and improve the electronic conductivity of the interface of the elastic component; the flexible sponge layer and the aluminum alloy sheet are bonded through the conductive adhesive to form an elastic part, and the surface of the aluminum alloy sheet is coated with the high-conductivity polyaniline and graphene mixed layer, so that the interface electronic conductivity between the flexible sponge layer and the aluminum alloy sheet can be effectively improved, and the internal resistance rise caused by micropores existing in the interface in the assembling process is avoided; thereby improving the electrochemical performance and the cycle life of the solid battery.
Preferably, Mg (NO) in step A)3)2·6H2O and Al (NO)3)3·9H2The molar ratio of O is 4-6:1-2, and the mass fraction of solute forming the mixed metal solution A is 2-5%; the molar ratio of the sodium hydroxide to the sodium carbonate is 1-1.5: 0.4-0.6.
Preferably, the alkaline solution B is dropwise added to the mixed metal solution A in the step B), and then the stirring is continued for 2-5h, the solid material is dried for 16-30 h, and the calcining temperature is 400-700 ℃.
Preferably, in the step C), the mass ratio of the metal filler particles to the aniline is 1-3:1-2.5, the ultrasonic time is 1-4 hours, and the mass ratio of the metal filler particles to the hydrochloric acid is 1-3: 0.3-0.5; the mass ratio of the aniline to the ammonium persulfate is 1-3: 1-2.5.
Preferably, in the step D), the flexible sponge layer is kept still for 24-48h, the drying temperature is 50-80 ℃, and the drying time is 12-24 h.
Preferably, in the step E), the electrolytic solution comprises 0.3-0.6mol/L sulfuric acid, 0.3-0.6mol/L aniline sulfate monomer and 0.02-0.1mol/L graphene, the plating voltage is a constant voltage of 1.3-1.6V, and the plating time is 20-45 minutes.
The invention also provides an application of the elastic component prepared by the method in an all-solid battery, wherein the solid battery comprises a positive plate, a solid electrolyte, a negative plate and a battery shell, the positive plate, the solid electrolyte, the negative plate and the battery shell are sequentially arranged, and the elastic component is attached and arranged between the positive plate and the solid electrolyte or between the negative plate and the solid electrolyte.
In addition, the elastic component is arranged between the solid electrolyte and the anode plate and the cathode plate, so that the mechanical integrity of the anode plate, the cathode plate and the solid electrolyte can be better protected, and the material deformation and the structural damage caused by volume expansion extrusion in the charging and discharging processes due to direct contact of the anode plate and the cathode plate and the solid electrolyte can be avoided.
Therefore, the invention has the following beneficial effects: (1) an elastic component for a solid battery, which integrates a polymer flexible sponge and a surface-treated metal base material, is designed, so that the elastic component has the flexibility of a polymer material and the high conductivity of a metal material;
(2) poor contact caused by volume change in the charge and discharge processes of the solid battery is buffered;
(3) an effective continuous electron transport path is ensured.
Drawings
Fig. 1 is a schematic view of the structure of an all-solid battery of example 1 of the invention.
Fig. 2 is a schematic structural view of an all-solid battery according to embodiment 2 of the present invention.
Fig. 3 is a schematic structural view of an all-solid battery according to embodiment 3 of the present invention.
In the figure: 1-elastic component, 11-aluminum alloy sheet, 12-flexible sponge layer, 2-positive plate, 3-solid electrolyte, 4-negative plate and 5-battery shell.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
an elastic component 1 comprises a flexible sponge layer 12 and an aluminum alloy sheet 11 which are arranged in an attaching mode; the flexible sponge layer is loaded with polyaniline and metal filler particles, the flexible sponge layer is made of polyurethane (460, Germany Kostew), the thickness of the flexible sponge layer is 2.5 mm, and the porosity is 45%; polyaniline and graphene are loaded on the surface of the aluminum alloy sheet, the thickness of the aluminum alloy sheet is 2.5 mm, and the mass fractions of other elements except aluminum in the aluminum alloy sheet are 4.46% of magnesium, 0.55% of manganese, 0.25% of iron, 0.14% of silicon, 0.1% of copper, 0.07% of chromium, 0.05% of nickel and 0.05% of zinc; the flexible sponge layer is bonded with the aluminum alloy sheet through conductive adhesive.
The preparation of the elastic component comprises the following steps:
A) mg (NO) with a molar ratio of 5:1.5 at room temperature3)2·6H2O and Al (NO)3)3·9H2Dispersing O in water, wherein the mass fraction of solute is 4%, and stirring the mixture under strong force until the solute is completely dissolved to form a mixed metal solution A; hydrogen and oxygen are mixedDispersing sodium chloride and sodium carbonate in water according to the molar ratio of 1.2:0.5 to obtain an alkaline solution B;
B) at room temperature, dropwise adding the alkaline solution B into the continuously stirred mixed metal solution A, continuously stirring for 3 hours after dropwise adding is completed, transferring the mixed solution into a high-pressure kettle after stirring is completed, carrying out heat treatment for 25 hours at 110 ℃, alternately washing for 4 times by using absolute ethyl alcohol and water after cooling, drying the solid material obtained after suction filtration in an oven at 65 ℃ for 24 hours, and finally calcining for 5 hours at 600 ℃ to obtain metal filler particles;
C) adding the metal filler particles obtained in the step B) and aniline into water according to the mass ratio of 2:1.8, performing ultrasonic dispersion for 3 hours at normal temperature to obtain uniformly dispersed colloidal suspension, then adding hydrochloric acid with the concentration of 2.0 mol/L into the suspension, wherein the mass ratio of the added metal filler to the hydrochloric acid is 2:0.4, then adding ammonium persulfate into the mixed solution, wherein the mass ratio of the aniline to the ammonium persulfate is 2:1.8, and continuously stirring for 45 minutes at 15 ℃ to obtain solution C;
D) immersing the flexible sponge layer into the solution C obtained in the step C), standing for 36 hours at 15 ℃ to ensure that the flexible sponge layer is fully contacted with the solution, taking out the immersed flexible sponge layer, washing with water for 4 times, and finally drying for 20 hours at 60 ℃ to obtain a flexible sponge layer loaded with polyaniline and metal fillers;
E) sealing the side surface of an aluminum alloy sheet by using epoxy resin, washing the upper surface and the lower surface of the aluminum alloy sheet for 3 times by using dilute nitric acid with the concentration of 0.15 mol/L, removing impurities and an oxide layer on the surface of the aluminum alloy sheet, then putting the aluminum alloy sheet into electrolyte which is stirred for 15 hours in advance, wherein the electrolyte contains 0.45 mol/L sulfuric acid, 0.45 mol/L aniline sulfate monomer and 0.06 mol/L graphene, and keeping the constant voltage for 37 minutes under the voltage of 1.5V to obtain the aluminum alloy sheet of which the surface is loaded with polyaniline and graphene;
F) and (3) selecting YC-03 type conductive adhesive, and bonding the flexible sponge layer loaded with polyaniline and metal filler in the step B) and the aluminum alloy sheet loaded with polyaniline and graphene on the surface obtained in the step E) together to obtain the elastic component of the flexible sponge layer/the aluminum alloy sheet/the flexible sponge layer.
The application of the elastic component in the all-solid battery comprises the following steps:
as shown in fig. 1, lithium iron phosphate is selected as a material of the positive plate 2, natural graphite is selected as a material of the negative plate 4, and the solid electrolyte 3 is selected as a polymer solid electrolyte, and in an environment with a water content of 7ppm and an oxygen content of 7ppm, the elastic members are respectively attached and arranged between the positive plate and the solid battery and between the negative plate and the solid battery, and then are packaged with the battery case 5 under a packaging pressure of 80 standard atmospheric pressures, so as to obtain the solid battery with the polyurethane/aluminum alloy plate.
Example 2:
an elastic component comprises a flexible sponge layer and an aluminum alloy sheet which are attached; the flexible sponge layer is loaded with polyaniline and metal filler particles, the flexible sponge layer is made of polytetrafluoroethylene (TF1641, American 3M), the thickness of the flexible sponge layer is 0.5 mm, and the porosity is 60%; polyaniline and graphene are loaded on the surface of the aluminum alloy sheet, the thickness of the aluminum alloy sheet is 5 mm, and the mass fractions of other elements except aluminum in the aluminum alloy sheet are 4.52% of magnesium, 0.5% of manganese, 0.25% of iron, 0.06% of silicon, 0.09% of copper, 0.03% of chromium, 0.05% of nickel and 0.02% of zinc; the flexible sponge layer is bonded with the aluminum alloy sheet through conductive adhesive.
The preparation of the elastic component comprises the following steps:
A) mg (NO) at room temperature in a molar ratio of 4:13)2·6H2O and Al (NO)3)3·9H2Dispersing O in water, wherein the mass fraction of solute is 2%, and stirring the mixture under strong force until the solute is completely dissolved to form a mixed metal solution A; dispersing sodium hydroxide and sodium carbonate in water according to the molar ratio of 1:0.4 to obtain an alkaline solution B;
B) at room temperature, dropwise adding the alkaline solution B into the continuously stirred mixed metal solution A, continuously stirring for 5 hours after dropwise adding is completed, transferring the mixed solution into a high-pressure kettle after stirring is completed, carrying out heat treatment for 30 hours at 100 ℃, alternately washing for 3 times by using absolute ethyl alcohol and water after cooling, drying the solid material obtained after suction filtration in an oven at 50 ℃ for 30 hours, and finally calcining for 4 hours at 700 ℃ to obtain metal filler particles;
C) adding the metal filler particles and aniline obtained in the step B) into water according to the mass ratio of 1:1, performing ultrasonic dispersion for 1 hour at normal temperature to obtain uniformly dispersed colloidal suspension, then adding hydrochloric acid with the concentration of 2.0 mol/L into the suspension, wherein the mass ratio of the added metal filler to the hydrochloric acid is 1:0.3, then adding ammonium persulfate into the mixed solution, wherein the mass ratio of the aniline to the ammonium persulfate is 1:1, and continuously stirring for 30 minutes at 15 ℃ to obtain solution C;
D) immersing the flexible sponge layer into the solution C obtained in the step C), standing for 48 hours at 5 ℃ to ensure that the flexible sponge layer is fully contacted with the solution, taking out the immersed flexible sponge layer, washing with water for 5 times, and finally drying for 24 hours at 50 ℃ to obtain the flexible sponge layer loaded with polyaniline and metal fillers;
E) sealing the side surface of an aluminum alloy sheet by using epoxy resin, washing the upper surface and the lower surface of the aluminum alloy sheet 4 times by using dilute nitric acid with the concentration of 0.15 mol/L, removing impurities and an oxide layer on the surface, then putting the aluminum alloy sheet into electrolyte which is stirred in advance for 20 hours, wherein the electrolyte contains 0.3 mol/L sulfuric acid, 0.3 mol/L aniline sulfate monomer and 0.1mol/L graphene, and keeping the constant voltage for 30 minutes under the voltage of 1.6 volts to obtain the aluminum alloy sheet of which the surface is loaded with polyaniline and graphene;
F) and (3) selecting YC-03 type conductive adhesive, and bonding the flexible sponge layer loaded with polyaniline and metal filler in the step B) and the aluminum alloy sheet loaded with polyaniline and graphene on the surface obtained in the step E) together to obtain the elastic component of the flexible sponge layer/aluminum sheet/flexible sponge layer.
The application of the elastic component in the all-solid battery comprises the following steps:
as shown in fig. 2, lithium manganate is selected as a material of the positive plate, a lithium plate is selected as a material of the negative plate, and a solid electrolyte is selected as an inorganic solid electrolyte, and in an environment with a water content of 6ppm and an oxygen content of 8ppm, the elastic member is attached and arranged between the positive plate and the solid electrolyte, and then the elastic member is packaged with the battery case 5 under a packaging pressure of 100 standard atmospheres, so as to obtain the solid battery with the polytetrafluoroethylene/aluminum alloy plate.
Example 3:
an elastic component comprises a flexible sponge layer and an aluminum alloy sheet which are attached; the flexible sponge layer is loaded with polyaniline and metal filler particles, the flexible sponge layer is made of polycarbonate (2095, Germany Bayer), the thickness of the flexible sponge layer is 5 mm, and the porosity is 30%; polyaniline and graphene are loaded on the surface of the aluminum alloy sheet, the thickness of the aluminum alloy sheet is 0.5 mm, and the mass fractions of other elements except aluminum in the aluminum alloy sheet are 4.4% of magnesium, 0.65% of manganese, 0.1% of iron, 0.14% of silicon, 0.04% of copper, 0.07% of chromium, 0.02% of nickel and 0.05% of zinc; the flexible sponge layer is bonded with the aluminum alloy sheet through conductive adhesive.
The preparation of the elastic component comprises the following steps:
A) mg (NO) with a molar ratio of 6:2 at room temperature3)2·6H2O and Al (NO)3)3·9H2Dispersing O in water, wherein the mass fraction of solute is 5%, and stirring the O under strong force until the O is completely dissolved to form a mixed metal solution A; dispersing sodium hydroxide and sodium carbonate in water according to the molar ratio of 1.5:0.6 to obtain an alkaline solution B;
B) at room temperature, dropwise adding the alkaline solution B into the continuously stirred mixed metal solution A, continuously stirring for 2 hours after dropwise adding is completed, transferring the mixed solution into a high-pressure kettle after stirring is completed, carrying out heat treatment for 20 hours at 120 ℃, alternately washing for 5 times by using absolute ethyl alcohol and water after cooling, drying the solid material obtained after suction filtration in an oven at 80 ℃ for 16 hours, and finally calcining for 7 hours at 400 ℃ to obtain metal filler particles;
C) adding the metal filler particles obtained in the step B) and aniline into water according to the mass ratio of 3:2.5, performing ultrasonic dispersion for 4 hours at normal temperature to obtain uniformly dispersed colloidal suspension, then adding hydrochloric acid with the concentration of 2.0 mol/L into the suspension, wherein the mass ratio of the added metal filler to the hydrochloric acid is 3:0.5, then adding ammonium persulfate into the mixed solution, wherein the mass ratio of the aniline to the ammonium persulfate is 3:2.5, and continuously stirring for 60 minutes at 15 ℃ to obtain solution C;
D) immersing the flexible sponge layer into the solution C obtained in the step C), standing for 24 hours at 20 ℃ to ensure that the flexible sponge layer is fully contacted with the solution, taking out the immersed flexible sponge layer, washing with water for 3 times, and finally drying for 12 hours at 80 ℃ to obtain a flexible sponge layer loaded with polyaniline and metal fillers;
E) sealing the side surface of an aluminum alloy sheet by using epoxy resin, washing the upper surface and the lower surface of the aluminum alloy sheet for 2 times by using dilute nitric acid with the concentration of 0.15 mol/L, removing impurities and an oxide layer on the surface, then putting the aluminum alloy sheet into electrolyte which is stirred for 10 hours in advance, wherein the electrolyte contains 0.6mol/L sulfuric acid, 0.6mol/L aniline sulfate monomer and 0.02 mol/L graphene, and keeping the constant voltage for 45 minutes under the voltage of 1.3V to obtain the aluminum alloy sheet loaded with polyaniline and graphene on the surface;
F) and (3) selecting YC-03 type conductive adhesive, and bonding the flexible sponge layer loaded with polyaniline and metal filler in the step B) and the aluminum alloy sheet loaded with polyaniline and graphene on the surface obtained in the step E) together to obtain the elastic component of the flexible sponge layer/the aluminum alloy sheet/the flexible sponge layer.
The application of the elastic component in the all-solid battery comprises the following steps:
as shown in fig. 3, a ternary material is selected as a material of the positive plate, a silicon-based negative plate is selected as a material of the negative plate, a solid electrolyte is selected as a polymer solid electrolyte, the elastic component is attached and arranged between the negative plate and the solid electrolyte in an environment with a water content of 8ppm and an oxygen content of 6ppm, and then the elastic component is packaged with the battery case 5 under a packaging pressure of 50 standard atmospheric pressures to obtain the solid battery with the polycarbonate/aluminum alloy plate.
Comparative example 1 (without elastic component)
The procedure of preparing the all-solid battery in comparative example 1 was the same as in example 1 to obtain a solid battery.
Comparative example 2 (elastic component only for aluminum alloy sheet processed)
The elastic member in comparative example 2 was an aluminum alloy sheet having a thickness of 2.5 mm, wherein the mass fractions of the elements other than aluminum in the alloy sheet were 4.46% magnesium, 0.55% manganese, 0.25% iron, 0.14% silicon, 0.1% copper, 0.07% chromium, 0.05% nickel, and 0.05% zinc.
The procedure of applying the elastic member to an all-solid battery was the same as in example 1, and a solid battery of an aluminum alloy sheet was finally obtained.
Comparative example 3 (elastic member not containing aluminum alloy sheet)
The elastic member in comparative example 3 was a flexible sponge layer loaded with polyaniline and metal filler particles, the flexible sponge layer was made of polyurethane (460, science, germany), the thickness of the flexible sponge layer was 2.5 mm, and the porosity was 45%.
Preparation of a flexible sponge layer loaded with polyaniline and metal filler particles, the procedure was the same as in example 1.
The procedure of applying the elastic member to an all-solid battery was the same as in example 1, and a polyurethane solid battery was finally obtained.
COMPARATIVE EXAMPLE 4 replacement of the Flexible sponge layer with rubber
An elastic component comprises rubber and an aluminum alloy sheet which are attached; the rubber is loaded with polyaniline and metal filler particles, the rubber is made of polyurethane (460, Germany Corsikon), and the thickness of the rubber is 2.5 mm; polyaniline and graphene are loaded on the surface of the aluminum alloy sheet, the thickness of the aluminum alloy sheet is 2.5 mm, and the mass fractions of elements except aluminum in the aluminum alloy sheet are 4.46% of magnesium, 0.55% of manganese, 0.25% of iron, 0.14% of silicon, 0.1% of copper, 0.07% of chromium, 0.05% of nickel and 0.05% of zinc; the flexible sponge layer is bonded with the aluminum alloy sheet through conductive adhesive.
The preparation of the elastic component comprises the following steps:
A) mg (NO) with a molar ratio of 5:1.5 at room temperature3)2·6H2O and Al (NO)3)3·9H2Dispersing O in water, wherein the mass fraction of solute is 4%, and stirring the mixture under strong force until the solute is completely dissolved to form a mixed metal solution A; dispersing sodium hydroxide and sodium carbonate in water according to the molar ratio of 1.2:0.5,obtaining an alkaline solution B;
B) at room temperature, dropwise adding the alkaline solution B into the continuously stirred mixed metal solution A, continuously stirring for 3 hours after dropwise adding is completed, transferring the mixed solution into a high-pressure kettle after stirring is completed, carrying out heat treatment for 25 hours at 110 ℃, alternately washing for 4 times by using absolute ethyl alcohol and water after cooling, drying the solid material obtained after suction filtration in an oven at 65 ℃ for 24 hours, and finally calcining for 5 hours at 600 ℃ to obtain metal filler particles;
C) adding the metal filler particles obtained in the step B) and aniline into water according to the mass ratio of 2:1.8, performing ultrasonic dispersion for 3 hours at normal temperature to obtain uniformly dispersed colloidal suspension, then adding hydrochloric acid with the concentration of 2.0 mol/L into the suspension, wherein the mass ratio of the added metal filler to the hydrochloric acid is 2:0.4, then adding ammonium persulfate into the mixed solution, wherein the mass ratio of the aniline to the ammonium persulfate is 2:1.8, and continuously stirring for 45 minutes at 15 ℃ to obtain solution C;
D) soaking the rubber into the solution C obtained in the step C), standing for 36 hours at 15 ℃ to ensure that the rubber is fully contacted with the solution, taking out the soaked rubber, washing with water for 4 times, and finally drying at 60 ℃ for 20 hours to obtain the rubber loaded with polyaniline and metal filler particles;
E) sealing the side surface of an aluminum alloy sheet by using epoxy resin, washing the upper surface and the lower surface of the aluminum alloy sheet for 3 times by using dilute nitric acid with the concentration of 0.15 mol/L, removing impurities and an oxide layer on the surface of the aluminum alloy sheet, then putting the aluminum alloy sheet into electrolyte which is stirred for 15 hours in advance, wherein the electrolyte contains 0.45 mol/L sulfuric acid, 0.45 mol/L aniline sulfate monomer and 0.06 mol/L graphene, and keeping the constant voltage for 37 minutes under the voltage of 1.5V to obtain the aluminum alloy sheet of which the surface is loaded with polyaniline and graphene;
F) and C, selecting YC-03 type conductive adhesive, and bonding the rubber loaded with polyaniline and metal filler particles in the step B) and the aluminum alloy sheet loaded with polyaniline and graphene on the surface obtained in the step E) together to obtain the rubber/aluminum alloy sheet/rubber elastic component.
The application of the elastic member in the all-solid battery, the procedure is the same as in example 1; finally obtaining the solid battery with the rubber/aluminum alloy sheet.
And (3) carrying out performance test on the assembled all-solid-state battery, wherein the performance test mainly comprises alternating current internal resistance and cycle life test, and the specific test conditions are as follows: at 30 ℃ and 60 ℃, in the voltage range of 3.0-4.1V, the battery is circulated by taking 0.1-0.3C as charge-discharge multiplying power until the battery has obvious short circuit (the voltage drop speed is more than or equal to 5 mV/S); the alternating current internal resistance of the battery is tested by using an alternating current impedance spectroscopy EIS, the applied voltage speed is 5mV, the frequency range is 1-106HZ, and the specific results obtained by the test are shown in Table 1.
TABLE 1 test results of solid-state batteries of different designs
Figure RE-GDA0003297101140000091
As can be seen from table 1, in example 1, the aluminum alloy sheet has not only good electronic conductivity but also good mechanical supporting effect; the surface of the aluminum alloy sheet is plated with graphene and polyaniline, so that the interface compatibility of the aluminum alloy sheet and the flexible sponge material is improved; the flexible sponge material has high electronic conductivity by integrating polyaniline and metal filler, has no obvious influence on the internal resistance of the battery, and the flexible characteristic of the flexible sponge material buffers the volume change of the materials of the positive and negative pole pieces in the charging and discharging process, so that the pole pieces are always in close contact with the solid electrolyte and the inside of the pole pieces, the generation of additional microscopic gaps at a solid/solid interface is avoided, the continuity of ion and electron transmission channels is ensured, the internal resistance and polarization loss of the battery are reduced, the capacity retention rate is increased, and the cycle life of the solid battery is prolonged. The cycle life of example 1 reached 246 weeks and 325 weeks, respectively, the cycle life of example 2 reached 241 weeks and 318 weeks, and the cycle life of example 3 reached 242 weeks and 322 weeks, respectively, at 30 ℃ and 60 ℃.
It can be seen from comparison of comparative example 1 with example 1 that the internal resistance of the solid-state battery of example 1 was not significantly increased, and the cycle life of the solid-state battery was relatively increased by 128 weeks and 146 weeks at 30 ℃ and 60 ℃, respectively, indicating that the elastic member of the present invention can indeed effectively improve the cycle life of the battery.
From comparison of comparative example 2 with example 1, it can be seen that the elastic member in comparative example 2 is an untreated aluminum alloy sheet which can reduce the internal resistance of the battery, but the cycle life of the solid battery of comparative example 2 is much shorter than that of the solid battery of example 1 due to lack of elasticity.
As can be seen from comparison between comparative example 3 and example 1, the elastic member in comparative example 3 is a polyurethane sponge, and due to the deformability of the flexible sponge layer and lack of support, the flexible sponge layer may fall off from the solid electrolyte or the positive and negative electrode sheets or be unevenly distributed at the latter stage of the cycle, resulting in an increase in polarization loss, and the cycle life of the battery was respectively reduced by 77 weeks and 85 weeks at 30 ℃ and 60 ℃ as compared to example 1.
It can be seen from comparison between example 1 and comparative example 4 that the cycle life of the solid battery of comparative example 4 was lower than that of the solid battery of example 1 because the cycle life of the solid battery of example 4 was lower than that of the solid battery of example 1 because the cycle life of the flexible sponge layer was increased by 10.1 Ω and the difference in internal resistance was insignificant, but the cycle life of the battery was reduced by 89 weeks and 107 weeks at 30 ℃ and 60 ℃ respectively, because the ordinary rubber was only partially swollen when immersed in the aniline solution, and only a small amount of the metal filler and polyaniline were impregnated into the rubber, compared to the flexible sponge layer of example 1, and the amount of the metal filler and polyaniline loaded in the ordinary rubber was insufficient to form a conductive interpenetrating network in the rubber.
The above results show that the invention proposes that the electrochemical performance and cycle life of the all-solid battery can be effectively improved by adding the elastic component integrating the high polymer material and the metal filler, and provides a reference path for the research of high-performance all-solid batteries.

Claims (10)

1. An elastic part is characterized by comprising a flexible sponge layer and an aluminum alloy sheet which are attached; the flexible sponge layer is loaded with polyaniline and metal filler particles, the surface of the aluminum alloy sheet is loaded with polyaniline and graphene, and the flexible sponge layer is bonded with the aluminum alloy sheet through conductive adhesive.
2. The elastic component of claim 1, wherein the flexible sponge layer has a thickness of 0.5-5 mm and a porosity of 30-60%, and is made of one or more materials selected from the group consisting of polyurethane, nylon, polytetrafluoroethylene and polycarbonate.
3. The elastic component of claim 1, wherein the aluminum alloy sheet has a thickness of 0.5-5 mm, and the aluminum alloy sheet further comprises one or more elements selected from magnesium, manganese, iron, silicon, copper, chromium, nickel and zinc in addition to aluminum.
4. A method for producing an elastic member according to any one of claims 1 to 3, comprising the steps of:
A) mixing Mg (NO)3）2·6H2O and Al (NO)3）3·9H2Dispersing O in water, and then stirring the mixture by a strong machine until the O is completely dissolved to form a mixed metal solution A; dispersing sodium hydroxide and sodium carbonate in water to form an alkaline solution B;
B) dripping the alkaline solution B into the mixed metal solution A under the condition of continuous stirring, after the stirring is finished, preserving the temperature of the mixed solution at the temperature of 100-120 ℃ for 20-30 hours, cooling, washing, filtering, drying the obtained solid material at the temperature of 50-80 ℃, and finally calcining in the air for 4-7 hours to obtain metal filler particles;
C) adding the metal filler particles and aniline into water, performing ultrasonic dispersion at normal temperature to obtain a colloidal suspension, then adding hydrochloric acid into the colloidal suspension, then continuously adding ammonium persulfate into the mixed solution, and stirring for 30-60 minutes at 5-20 ℃ to obtain a solution C;
D) immersing the flexible sponge layer into the solution C, standing at 5-20 ℃, taking out the immersed flexible sponge layer, washing and drying to obtain the flexible sponge layer loaded with polyaniline and metal filler particles;
E) sealing the side surface of the aluminum alloy sheet by using insulating resin, washing the upper surface and the lower surface of the aluminum alloy sheet by using dilute nitric acid, and then putting the aluminum alloy sheet into an electrolytic solution which is stirred in advance for 10-20h for electroplating to obtain the aluminum alloy sheet of which the surface is loaded with polyaniline and graphene;
F) and D), bonding the flexible sponge layer loaded with the polyaniline and the metal filler particles in the step D) and the aluminum alloy sheet loaded with the polyaniline and the graphene on the surface in the step E) by using a conductive adhesive to obtain the elastic component.
5. The process for producing an elastic member according to claim 4, wherein Mg (NO) is contained in the step A)3）2·6H2O and Al (NO)3）3·9H2The molar ratio of O is 4-6:1-2, and the solute mass fraction of the mixed metal solution A is 2-5%; the molar ratio of the sodium hydroxide to the sodium carbonate is 1-1.5: 0.4-0.6.
6. The method according to claim 4, wherein the alkali solution B is added dropwise to the mixed metal solution A in step B) and the mixture is stirred for 2-5h, the solid material is dried for 16-30 h, and the calcination temperature is 400-700 ℃.
7. The method according to claim 4, wherein in step C), the mass ratio of the metal filler particles to the aniline is 1-3:1-2.5, the ultrasonic treatment time is 1-4 hours, and the mass ratio of the metal filler particles to the hydrochloric acid is 1-3: 0.3-0.5; the mass ratio of the aniline to the ammonium persulfate is 1-3: 1-2.5.
8. The method of claim 4, wherein in step D), the flexible sponge layer is allowed to stand for 24-48 hours, dried at 50-80 ℃ for 12-24 hours.
9. The method as claimed in claim 4, wherein in the step E), the electrolytic solution comprises 0.3-0.6mol/L sulfuric acid, 0.3-0.6mol/L aniline sulfate monomer and 0.02-0.1mol/L graphene, the plating voltage is a constant voltage of 1.3-1.6V, and the plating time is 20-45 minutes.
10. The use of the elastic member according to any one of claims 1 to 3 in an all-solid battery, wherein the solid battery comprises a positive electrode sheet, a solid electrolyte and a negative electrode sheet arranged in sequence, and the elastic member is arranged between the positive electrode sheet and the solid electrolyte or between the negative electrode sheet and the solid electrolyte in an attaching manner.
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Publication number Priority date Publication date Assignee Title
CN108624907A (en) * 2018-04-26 2018-10-09 复旦大学 Nonmetal basal body efficient catalytic electrode and preparation method thereof
KR20200009583A (en) * 2018-07-19 2020-01-30 김영훈 Low-resistance conductive tapes for aluminium material enhancing radio frquency, having excellent resistance to galvanic corrosion and oxidation
JP2021034141A (en) * 2019-08-19 2021-03-01 三洋化成工業株式会社 Lithium ion battery module and battery pack
JP2021082391A (en) * 2019-11-14 2021-05-27 三洋化成工業株式会社 Lithium-ion battery module and battery pack

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108624907A (en) * 2018-04-26 2018-10-09 复旦大学 Nonmetal basal body efficient catalytic electrode and preparation method thereof
KR20200009583A (en) * 2018-07-19 2020-01-30 김영훈 Low-resistance conductive tapes for aluminium material enhancing radio frquency, having excellent resistance to galvanic corrosion and oxidation
JP2021034141A (en) * 2019-08-19 2021-03-01 三洋化成工業株式会社 Lithium ion battery module and battery pack
JP2021082391A (en) * 2019-11-14 2021-05-27 三洋化成工業株式会社 Lithium-ion battery module and battery pack

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