CN117276647A - Solid-state battery and preparation method and application thereof - Google Patents

Solid-state battery and preparation method and application thereof Download PDF

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CN117276647A
CN117276647A CN202311430249.1A CN202311430249A CN117276647A CN 117276647 A CN117276647 A CN 117276647A CN 202311430249 A CN202311430249 A CN 202311430249A CN 117276647 A CN117276647 A CN 117276647A
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solid
state battery
negative electrode
oxide
electrolyte
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邵俊华
张利娟
李海杰
张勇来
林召强
李强
马玉柱
陈亮
陀家明
方钰滢
熊小寒
林凤芝
张永辉
廖余涛
田斌
邵家磊
邱燕妮
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Liuzhou Fansaike New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of batteries, and particularly relates to a solid-state battery, and a preparation method and application thereof. The solid-state battery comprises a positive plate, a negative plate and a solid electrolyte positioned between the positive plate and the negative plate; the negative electrode plate comprises a negative electrode solid component, wherein the negative electrode solid component comprises a base material and a coating layer, the base material comprises an oxide and a few layers of MXene, and the coating layer is a carbon coating layer; the preparation raw materials of the solid electrolyte comprise oxide solid electrolyte, polyoxyethylene, polybenzimidazole and lithium salt; wherein, the polybenzimidazole accounts for 2 to 5 percent of the mass of the polyethylene oxide. The solid-state battery is favorable for the transmission of electrons and ions, can bear larger multiplying power charge and discharge, can improve the capacity retention rate, and shows good electrochemical performance.

Description

Solid-state battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a solid-state battery, and a preparation method and application thereof.
Background
The main current battery used in the market at present is a traditional battery, which adopts liquid electrolyte, and potential safety hazards such as liquid leakage, ignition and explosion exist. Compared with the traditional battery, the improved part of the solid-state battery mainly comprises the liquid electrolyte which is changed into the solid state, so that the solid-state battery has the advantages of no leakage, good thermal stability, no volatilization, low spontaneous combustion or explosion risk and the like, and the solid-state battery also has the advantages of larger energy density improving space, higher safety, wide application temperature range and the like, so that the solid-state battery becomes the next-generation energy storage technology with wide application prospect. However, solid-state batteries also face a number of challenges in practical applications. The main problem is that the interface in the solid-state battery has physical contact and chemical contact, the ion of the traditional lithium battery is contacted with the electrode in the liquid, the electrolyte and the electrode of the solid-state battery are all solid, the wetting degree of the contact surface is low, the contact resistance is easy to be increased due to the reaction in the charging and discharging process, and the heat is increased. In addition, during discharge, a resistive film is formed at the interface between the positive electrode active material and the solid electrolyte, resulting in a decrease in output density.
Therefore, improvements in the interface between the solid electrolyte and the battery electrode are needed to obtain a solid battery with better electrochemical performance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a solid-state battery, and a preparation method and application thereof. The solid-state battery is favorable for the transmission of electrons and ions, can bear larger multiplying power charge and discharge, can improve the capacity retention rate (more than 90 percent), and shows good electrochemical performance.
In a first aspect of the present invention, there is provided a solid-state battery including a positive electrode sheet, a negative electrode sheet, and a solid electrolyte between the positive electrode sheet and the negative electrode sheet;
the negative electrode sheet comprises a negative electrode solid component, wherein the negative electrode solid component comprises a base material and a coating layer, the base material comprises an oxide and a few-layer MXene, and the coating layer is a carbon coating layer;
the preparation raw materials of the solid electrolyte comprise oxide solid electrolyte, polyoxyethylene, polybenzimidazole and lithium salt; wherein the polybenzimidazole accounts for 2 to 5 percent of the mass of the polyethylene oxide.
(1) The MXene material has good electrical conductivity. In terms of electron mobility, due toThe lamellar structure of the MXene material confines M atoms and the like within the layer, allowing electrons to migrate smoothly between layers. In addition, it has the characteristics of small volume change and high capacity. However, the aggregation and accumulation of MXene sheets can lead to slow metal ion migration rates and thus affect the rate performance of the battery. Oxides, e.g. Co 3 O 4 When used as an electrode material, the electrolyte material has excellent energy storage performance, but has the problems of poor conductivity, serious volume expansion/shrinkage in the charge and discharge process, unstable phase mode (SEI) formed between the electrode material and the solid electrolyte, and the like, thereby causing obvious irreversible capacity loss and poor cycle stability. MXnes with Co 3 O 4 Combining to obtain Co 3 O 4 @Ti 3 C 2 Tx composite material capable of suppressing volume expansion of metal oxide, ti 3 C 2 Tx/Co 3 O 4 The interfacial Co-O-Ti interaction also effectively limits Co 3 O 4 Is used for preventing Co from growing 3 O 4 From Ti during circulation 3 C 2 Tx surface drop, facilitate Co 3 O 4 And Ti is 3 C 2 T x Interface electron transfer between the two; and also prevents aggregation and stacking of mxnes nanoplatelets. The structure combines well the conductivity of mxnes and the high capacity properties of metal oxides, which structure gives a significant improvement in electrochemical properties, especially in terms of storage performance, high rate and long cycle stability.
In addition, because mxnes surfaces have a large number of exposed metal atoms, their surface energy is generally high and poor oxygen resistance in air results in a great loss of their electronic properties and surface reactivity. The capping effect and reducibility of the carbon nanocladding effectively limit surface oxidation and structural degradation of mxnes.
Carbon coating, MXene and Co 3 O 4 The synergistic effect of the three components greatly improves the electrochemical performance, the structural stability and the electrochemical reaction dynamics of the negative plate, and ensures the rapid charge transfer and the high structural stability.
(2) In the case of a solid electrolyte, the addition of an oxide solid electrolyte effectively suppresses the crystallinity of polyethylene oxide. The reason for this phenomenon may be that the addition of the oxide solid electrolyte reduces the ordering of the polyethylene oxide, increases the amorphous phase ratio in the polyethylene oxide matrix, thereby increasing the segmental motion of the polyethylene oxide, facilitating the migration of lithium ions, and resulting in an increase in the ionic conductivity of the electrolyte. The polybenzimidazole can effectively promote the dissociation of lithium salt to generate more free lithium ions, thereby further improving the ion conductivity.
(3) The solid electrolyte provided by the invention is matched with the solid components of the negative electrode, and has the effects of increasing interface contact and synergistically enhancing ion transmission.
The small-layer MXene refers to a sheet material with MXene layers below 10 layers.
In some embodiments of the invention, the oxide is selected from Co 3 O 4 、Fe 3 O 4 、GeO 2 、SiO 2 At least one of (a) and (b); co is preferred 3 O 4 。
In some embodiments of the invention, the MXene is selected from Ti 3 C 2 T x 、Ti 2 CT xx 、Nb 3 C 2 T x 、V 2 CT x 、V 3 C 2 T x At least one of (a) and (b); preferably Ti 3 C 2 T、Ti 2 CT xx 。
In some embodiments of the invention, the carbon coating layer has a thickness of 5 to 500nm; preferably 30 to 300nm.
The preparation method of the negative electrode solid component comprises the following steps:
mixing oxide, a few MXene layers and glucose, performing hydrothermal reaction, drying and annealing to obtain the composite material.
The carbon coating on MXene is achieved by hydrothermal carbonization of glucose. In this process, glucose molecules preferentially adsorb on the surface of MXene, reducing its surface free energy by hydrogen bonding interactions between its oxygen-containing groups. They are then converted under hydrothermal conditions into hydrothermal carbon by intermolecular polymerization and in situ into a more conductive carbon layer on the surface of the MXene by thermal carbonization.
Wherein the mass ratio of the oxide to the MXene is 5-20: 1, a step of;
the mass ratio of glucose to MXene is 5-15: 1, a step of;
the temperature of the hydrothermal reaction is 120-200 ℃; the hydrothermal reaction time is 12-48 h;
the annealing process is carried out under the protection of argon, the annealing temperature is 450-600 ℃, and the annealing time is 1-4 h.
The few-layer MXene can be prepared by adopting the prior method in the field, for example, the MXenes prepared by an HCl solution and fluoride-based salt etching method in the invention contain more-O-, -OH and-F, and the functional groups have a certain influence on the energy storage performance of the material.
In some embodiments of the invention, the method of preparing the few-layer MXene comprises the steps of:
the multi-layer MXene is prepared by adopting a chemical etching method, and then the few-layer MXene is prepared by adopting an ultrasonic stripping method.
Specifically, 20-40 mL of 6-10 mol/L HCl solution is mixed with 2-4 g LiF for 20-60 min. Then slowly adding 1-3 g Ti 3 AlC 2 Stirring for 24-48 h at 20-50 ℃. Centrifuging, washing until the pH value of the solution is close to neutral, and drying to obtain powder. Taking 0.5-2 g of the powder in 30-60 mL of DMSO, stirring for 8-12 hours at 20-50 ℃, centrifuging, washing and drying to obtain a precipitate. Dispersing the precipitate in 50-200 mL of water, carrying out ultrasonic treatment for 1-4 h under the conditions of argon atmosphere and ice bath, centrifuging, taking filtrate, and drying to obtain the product.
The invention prepares a few-layer MXene nano-sheet by using a DMSO intercalation method, and DMSO intercalates Ti 3 C 2 T x The interlayer spacing is enlarged, and after ultrasonic treatment, DMSO intercalated Ti 3 C 2 T x Dispersing into a few-layered sheet in water; ti is filtered by vacuum 3 C 2 T x When the sheet is used for storing energy of a lithium ion battery, the sheet has higher specific capacity under certain current density.
In some embodiments of the invention, the negative electrode sheet further comprises a negative electrode active material, the negative electrode active material being graphite.
In some embodiments of the present invention, the negative electrode sheet further includes a negative electrode conductive agent selected from at least one of acetylene black, carbon nanotubes, graphene, conductive graphite, conductive carbon black, ketjen black, and carbon fibers.
In some embodiments of the invention, the negative electrode sheet further comprises a negative electrode binder selected from at least one of polyvinylidene fluoride and/or polytetrafluoroethylene.
In some embodiments of the invention, the negative electrode sheet further comprises a negative electrode collector selected from copper foil or stainless steel mesh.
The negative electrode active material, the negative electrode solid component, the negative electrode conductive agent, and the negative electrode binder of the present invention constitute a negative electrode active material layer that is provided on the negative electrode current collector.
In some embodiments of the present invention, the mass ratio of the negative electrode active material, the negative electrode solid component, the negative electrode conductive agent, and the negative electrode binder is (88-95): 1-10): 1-5.
In some embodiments of the present invention, the solvent used in the preparation process of the negative electrode sheet includes any one or a combination of at least two of acetonitrile, dimethylformamide, dimethylacetamide or N-methylpyrrolidone, but is not limited to the above-listed solvents, and other solvents commonly used in the art to achieve the same effect may be used in the present invention.
In some embodiments of the present invention, the solvent is added in an amount of 10% -60% of the mass of the positive electrode during the preparation of the negative electrode sheet.
In some embodiments of the invention, the positive electrode sheet comprises a positive electrode active material selected from the group consisting of LiCoO 2 、LiMn 2 O 4 、LiFePO 4 、LiMnPO 4 、LiVPO 4 At least one of them.
In some embodiments of the present invention, the positive electrode sheet further includes a conductive agent including at least one selected from acetylene black, carbon nanotubes, fullerenes, or carbon fibers, but is not limited to the above-listed conductive agents, and other conductive agents commonly used in the art may be used in the present invention.
In some embodiments of the present invention, the positive electrode sheet further includes a binder selected from at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), or styrene-butadiene rubber (SBR).
In some embodiments of the invention, the positive electrode sheet further comprises a positive electrode current collector that is aluminum foil.
The positive electrode active material, the positive electrode conductive agent, and the positive electrode binder of the present invention constitute a positive electrode active material layer that is provided on the positive electrode current collector.
In some embodiments of the present invention, the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is (88-95): 1-10.
In some embodiments of the present invention, the solvent used in the preparation process of the positive electrode sheet includes at least one of acetonitrile, dimethylformamide, dimethylacetamide or N-methylpyrrolidone, but is not limited to the above-listed solvents, and other solvents commonly used in the art to achieve the same effect may be used in the present invention.
In some embodiments of the present invention, the solvent is added in an amount of 10% -60% of the mass of the positive electrode during the preparation of the positive electrode sheet.
In some embodiments of the invention, the oxide solid state electrolyte is selected from at least one of LLZO, LLZTO, LZTO, LLTO.
Garnet-type electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) room temperature conductivity is typically 10 -3 ～10 -4 S/cm, higher than polymers and other oxide electrolytes, and LLZO is relatively stable in contact with lithium.
In some embodiments of the invention, the oxide solid state electrolyte has a particle size in the range of 100 to 300nm.
The powder particle size of the oxide solid electrolyte is smaller, the impedance provided by the powder is reduced, and the impedance of the electrolyte is relatively reduced.
In some embodiments of the invention, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium perchlorate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonimide, lithium bistrifluorosulfonylimide.
In some embodiments of the invention, the mass ratio of the oxide solid electrolyte to polyethylene oxide is 1:1.5 to 5.
The proper mass ratio of the oxide solid electrolyte to the polyethylene oxide is advantageous for improving the ionic conductivity of the electrolyte, whereas, for example, when the oxide solid electrolyte is excessively added, particles are easy to agglomerate, so that interface impedance between the oxide solid electrolytes and the polyethylene oxide is increased, and the ionic conductivity of the electrolyte is reduced.
In some embodiments of the invention, the polyethylene oxide has a molar ratio of ethylene oxide to lithium ions in the lithium salt of 15 to 20:1.
in some embodiments of the present invention, the method of preparing a solid electrolyte includes the steps of:
stirring the oxide solid electrolyte, polyethylene oxide (PEO) and lithium salt for 10-16 h at 20-30 ℃, adding Polybenzimidazole (PBI) and stirring for 2-6 h at 20-30 ℃, and drying to obtain the final product.
In a second aspect of the present invention, there is provided a method for preparing the above solid-state battery, wherein the solid-state battery is assembled from the positive electrode sheet, the solid electrolyte and the negative electrode sheet.
In some embodiments of the invention, the assembly process is performed under an inert gas atmosphere.
In a third aspect of the invention there is provided the use of a solid state battery as described above in an energy storage device.
The energy storage device comprises a small energy storage device, a large energy storage device and a high-temperature energy storage device.
Preferably, the small-sized energy storage device comprises a mobile phone, a notebook computer and a charger.
Preferably, the large energy storage device comprises an electric automobile and a large energy storage power station.
The solid-state battery according to the embodiment of the invention has at least the following advantageous effects:
the solid-state battery is favorable for the transmission of electrons and ions, can bear larger multiplying power charge and discharge, can improve the capacity retention rate (more than 90 percent), and shows good electrochemical performance.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Examples
Polyethylene oxide (PEO) used in the present invention was purchased from aladin, and the Mw (relative molecular mass) was 600000.
LiTFSI used in the present invention was purchased from Sigma Aldrich.
Example 1
The embodiment provides a solid-state battery, which comprises a positive plate, a negative plate and a solid-state electrolyte positioned between the positive plate and the negative plate. Wherein,
(1) The positive plate is formed by coating positive electrode slurry on a current collector and then rolling and tabletting, wherein the positive electrode slurry contains lithium iron phosphate (LiFePO) 4 ) The conductive carbon black (super P) and PVDF are sequentially 90%,5% and 5% by weight based on the total mass of the three components.
(2) The negative plate is formed by coating negative electrode slurry on a current collector and then rolling the negative electrode slurry, wherein the negative electrode slurry comprises Co with a carbon nano coating layer 3 O 4 /Ti 3 C 2 -MXene, graphite, conductive carbon black, polyvinylidene fluoride (PVDF), each composition being 2.5%, 94.5%,1% and 2% in order of 100% by mass of the total of these four terms.
(3) The solid electrolyte is prepared from lanthanum lithium zirconate (Li 7 La 3 Zr 2 O 12 LLZO), PEO, polybenzimidazole (PBI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI).
The preparation method of the solid-state battery specifically comprises the following steps:
1. the preparation method of the positive electrode plate comprises the following steps:
weighing LiFePO 4 Adding super P and PVDF into N-methyl pyrrolidone, magnetically stirring for 16h, spreading the obtained uniform slurry on a dry aluminum foil by using a scraper, drying the coated pole piece at 80 ℃ until the quality is not changed, rolling, and die cutting to obtain the compact density of 2.1g/cm 3 Is a positive electrode sheet of the battery.
2. The preparation method of the negative electrode plate comprises the following steps:
2.1 preparation method of few MXene layers:
preparing a plurality of layers of MXene by adopting a chemical etching method, and preparing a few layers of MXene by adopting an ultrasonic stripping method, and specifically:
30mL of 9mol/L HCl solution were first measured and mixed with 3g of LiF for 40min. Then, 2.0g of Ti was slowly added 3 AlC 2 The powder was stirred at 40℃for 36 hours. The resulting multi-layered MXene was centrifuged to remove the etchant and repeatedly washed with deionized water until the pH of the solution was near neutral. The washed solution was freeze-dried for 24 hours to obtain a powder. 1g of the above powder was weighed into 40mL of DMSO and then stirred at 40℃for 10 hours. Next, the intercalated MXene solution was centrifuged at 7500r/min, washed well, dried in a vacuum oven at 60℃for 8 hours, and cooled to room temperature to obtain a precipitate. The resulting precipitate was dispersed in 100mL of water and sonicated under argon atmosphere and ice bath conditions for 2h to convert the multi-layer MXene to a few-layer MXene. Centrifuging at 3500r/min, collecting filtrate, and freeze drying to obtain small-layer MXene sheet material with layer number below 10.
2.2MXene composite material preparation method:
150mg CoSO 4 ·7H 2 O, 135mg of 5-sulfosalicylic acid and 70mg of glutaric acid are dissolved in 50mL of deionized water, and the pH value of the solution is adjusted toAbout 7.0. Then 100mg of glucose and 10mg of the less MXene prepared in step 2.1 were added. The mixed solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and reacted hydrothermally at 160 ℃ for 24 hours. Washing the obtained product with deionized water through several centrifugal-rinsing cycles, freeze-drying, and annealing at 500 ℃ for 2 hours under the protection of argon gas at the heating rate of 2 ℃/min to obtain Co with carbon coating 3 O 4 /Ti 3 C 2 -MXene material. The thickness of the carbon coating layer was measured to be 30 to 300nm.
2.3 preparation method of negative electrode plate:
co with carbon coating 3 O 4 /Ti 3 C 2 The MXene material, graphite, conductive carbon black and polyvinylidene fluoride are fully stirred and uniformly mixed in deionized water according to a proportion to form negative electrode active slurry, the negative electrode active slurry is coated on the surface of copper foil, the coated pole piece is dried at 80 ℃ until the quality is not changed, and then the pole piece is rolled and die-cut to obtain the compact density of 0.8g/cm 3 Is a negative electrode plate.
3. The preparation method of the solid composite polymer electrolyte comprises the following steps:
the solid composite polymer electrolyte is prepared by adopting a solution casting method.
0.5g of LLZO powder with the particle size ranging from 0.1 to 0.3 mu m is added into 50mL of N-methylpyrrolidone, and the mixture is dispersed by ultrasonic. PEO (1.5 g) and lithium salt (LiTFSI) were combined as Ethylene Oxide (EO) in PEO with lithium ion (Li) in lithium salt + ) PEO was weighed and LiTFSI was added to the solution in a molar ratio of 18:1. Stirring at room temperature for 12h, to obtain a uniform electrolyte slurry. And then adding Polybenzimidazole (PBI) with the mass fraction of 3% relative to PEO, magnetically stirring for 4 hours, casting on a polytetrafluoroethylene mould, and vacuum drying at 60 ℃ for 24 hours to obtain the solid composite polymer electrolyte by stripping.
Finally, the solid-state battery of this embodiment is assembled into a CR 2032-type button battery from a positive electrode sheet, a solid-state electrolyte, and a negative electrode sheet.
Example 2
The embodiment provides a solid-state battery, which comprises a positive plate, a negative plate and a solid-state electrolyte positioned between the positive plate and the negative plate. Wherein,
(1) The positive plate is formed by coating positive electrode slurry on a current collector and then rolling and tabletting, wherein the positive electrode slurry contains LiFePO 4 The conductive carbon black and PVDF are sequentially 91.5%,4.5% and 4% by weight based on 100% of the total mass of the three components.
(2) The negative plate is formed by coating negative electrode slurry on a current collector and then rolling the negative electrode slurry, wherein the negative electrode slurry comprises Co with a carbon nano coating layer 3 O 4 /Ti 3 C 2 The proportion of the components is 2%, 95%,1.5% and 1.5% based on 100% of the total mass of the four components.
(3) The solid electrolyte is prepared from LLZO, PEO, PBI, liTFSI.
The preparation method of the solid-state battery specifically comprises the following steps:
1. the preparation method of the positive electrode plate comprises the following steps:
reference is made to "1. Preparation method of positive electrode sheet" in example 1.
2. The preparation method of the negative electrode plate comprises the following steps:
2.1 preparation method of few MXene layers:
reference is made to example 1 under "preparation method of 2.1 few layer MXene".
2.2MXene composite material preparation method:
200mg CoSO 4 ·7H 2 O, 160mg of 5-sulfosalicylic acid and 90mg of glutaric acid are dissolved in 50mL of deionized water, and the pH value of the solution is adjusted to about 7.0. 100mg of glucose and 12mg of the less MXene prepared in step 2.1 were added. The mixed solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and reacted hydrothermally at 170 ℃ for 20 hours. Washing the obtained product with deionized water through several times of centrifugal-rinsing cycles, freeze-drying, and annealing at 450 ℃ for 2 hours under the protection of argon gas at the heating rate of 2 ℃/min to obtain Co with a carbon coating layer 3 O 4 /Ti 3 C 2 -MXene material. Carbon coating was measuredThe thickness of the layer is 30-300 nm.
2.3 preparation method of negative electrode plate:
reference is made to the "preparation method for 2.3 negative electrode sheet" in example 1.
3. The preparation method of the solid composite polymer electrolyte comprises the following steps:
the solid composite polymer electrolyte is prepared by adopting a solution casting method.
0.5g of LLZO powder with the particle size ranging from 0.1 to 0.3 mu m is added into 50mL of N-methylpyrrolidone, and the mixture is dispersed by ultrasonic. PEO (2 g) and lithium salt (LiTFSI) were combined as Ethylene Oxide (EO) in PEO with lithium ion (Li) in lithium salt + ) PEO was weighed and LiTFSI was added to the solution in a molar ratio of 20:1. Stirring at room temperature for 8h, to obtain a uniform electrolyte slurry. And then adding Polybenzimidazole (PBI) with the mass fraction of 2% relative to PEO, magnetically stirring for 6 hours, casting on a polytetrafluoroethylene mould, and vacuum drying at 60 ℃ for 24 hours to obtain the solid composite polymer electrolyte by stripping.
Finally, the solid-state battery of this embodiment is assembled into a CR2032 type button full battery from a positive electrode sheet, a solid-state electrolyte, and a negative electrode sheet.
Comparative example 1
Referring to example 1, the difference is that: the few layer MXene is replaced with a multi-layer MXene. That is to say,
2.1 the preparation method of the multilayer MXene comprises the following steps:
the method adopts a chemical etching method to prepare a plurality of layers of MXene, in particular:
30mL of 9mol/L HCl solution were first measured and mixed with 3g of LiF for 40min. Then, 2.0g of Ti was slowly added 3 AlC 2 The powder was stirred at 40℃for 36 hours. The resulting multi-layered MXene was centrifuged to remove the etchant and repeatedly washed with deionized water until the pH of the solution was near neutral. The washed solution was freeze-dried for 24 hours to obtain a powder.
Comparative example 2
Referring to example 1, the difference is that: the default carbon coating, i.e.,
2.2MXene composite material preparation method:
150mg CoSO 4 ·7H 2 O, 135mg of 5-sulfosalicylic acid and 70mg of glutaric acid are dissolved in 50mL of deionized water, and the pH value of the solution is adjusted to about 7.0. 10mg of the less layer MXene prepared in step 2.1 were added. The mixed solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and reacted hydrothermally at 160 ℃ for 24 hours. Washing the obtained product with deionized water through several centrifugal-rinsing cycles, freeze-drying, and annealing at 500 ℃ for 2 hours under the protection of argon gas at the heating rate of 2 ℃/min to obtain Co 3 O 4 /Ti 3 C 2 -MXene material.
Comparative example 3
Referring to example 1, the difference is that: default Co 3 O 4 I.e.,
2.2MXene composite material preparation method:
100mg of glucose and 10mg of the small layer of MXene prepared in step 2.1 were dissolved in 50mL of deionized water, and the pH of the solution was adjusted to about 7.0. The mixed solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and reacted hydrothermally at 160 ℃ for 24 hours. The obtained product is washed by a plurality of centrifugal-rinsing cycles with deionized water, is frozen and dried, and is annealed for 2 hours at 500 ℃ under the protection of argon gas at the heating rate of 2 ℃/min.
Comparative example 4
Referring to example 1, the difference is that: default carbon coating and Co 3 O 4 I.e.,
2.2MXene composite material preparation method:
10mg of the small-layer MXene prepared in the step 2.1 was dissolved in 50mL of deionized water, and the pH of the solution was adjusted to about 7.0. The mixed solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave and reacted hydrothermally at 160 ℃ for 24 hours. The obtained product is washed by a plurality of centrifugal-rinsing cycles with deionized water, is frozen and dried, and is annealed for 2 hours at 500 ℃ under the protection of argon gas at the heating rate of 2 ℃/min.
Comparative example 5
Referring to example 1, the difference is that: and a default oxide solid state electrolyte LLZO.
Comparative example 6
Referring to example 1, the difference is that: default polyethylene oxide.
Comparative example 7
Referring to example 1, the difference is that: polyethylene oxide is replaced by polymethyl methacrylate (PMMA).
Comparative example 8
Referring to example 1, the difference is that: the mass fraction of polybenzimidazole was 10% relative to PEO.
Test case
The performance parameters of the solid electrolyte prepared according to the present invention are shown in table 1.
Table 1 performance parameters of the solid electrolytes of examples 1 and 2 and comparative examples 1 to 8
Conductivity (S/cm) of solid electrolyte
Example 1 5.6×10 -3
Example 2 1.9×10 -3
Comparative example 1 5.6×10 -3
Comparative example 2 5.6×10 -3
Comparative example 3 5.6×10 -3
Comparative example 4 5.6×10 -3
Comparative example 5 4.2×10 -6
Comparative example 6 7.3×10 -5
Comparative example 7 6.7×10 -4
Comparative example 8 1.6×10 -4
The performance parameters of the solid-state batteries prepared according to the present invention are shown in table 2. The specific capacity of the first discharge in the charge-discharge process at 0.01V-3V and 0.1C multiplying power is calculated, and after the cycle is 5 circles at 0.1C multiplying power, the multiplying power performance is tested by 100 circles at 0.2C multiplying power.
Table 2 performance parameters of solid-state batteries of examples 1, 2 and comparative examples 1 to 8
As can be seen from the data in tables 1 and 2, the present invention shows excellent conductivity by the combined use of the oxide solid electrolyte, PEO, and PBI. The solid-state battery is more favorable for the transmission of electrons and ions, can bear larger multiplying power charge and discharge, can improve the capacity retention rate (more than 90 percent), and shows good electrochemical performance.
As can be seen from a comparison of example 1 and comparative example 1: replacement of a few layer of MXene with a multiple layer of MXene results in a decrease in electrochemical performance of the solid state battery. The reasons may be that: the collapse and accumulation of the layered structure of the multi-layered mxnes material occurs during the fabrication process, resulting in a substantial reduction in contact area, thereby reducing the electron and ion transport capabilities of the mxnes material in the direction perpendicular to the layered structure. Layering multiple layers of mxnes particles to produce a "paper" like few layer structure is therefore a strategy to improve the electrochemical properties of the material.
As can be seen from a comparison of example 1 with comparative example 2: the default carbon coating may result in reduced electrochemical performance of the solid state battery. The reasons may be that: under the protection of the carbon coating layer, the MXene can not generate morphological and texture damage in the whole hydrothermal reaction and high-temperature annealing process. The reducibility of carbonaceous materials also helps to mitigate oxidation phenomena.
As can be seen from a comparison of example 1 with comparative example 3: default Co 3 O 4 Resulting in degradation of electrochemical performance of the solid-state battery. The reasons may be that: default Co 3 O 4 After that, the MXnes nano-sheets are aggregated and stacked, and the metal conductivity of the MXnes is reduced.
As can be seen from a comparison of example 1 with comparative example 4: default carbon coating and Co 3 O 4 Further, the electrochemical performance of the solid-state battery may be degraded. The reasons may be that: aggregation and stacking readily occurs in the presence of only mxnes nanoplatelets, and absent protection of the carbon coating, mxnes suffer morphological and texture damage throughout the hydrothermal reaction and high temperature annealing process.
As can be seen from a comparison of example 1 with comparative examples 5, 6, respectively: either the default oxide solid state electrolyte or the polyethylene oxide may cause a decrease in the electrochemical performance of the solid state battery. The reasons may be that: the polyethylene oxide electrolyte has better flexibility and lower interface impedance between the electrode and the electrolyte. Omitting polyethylene oxide, only the presence of an oxide solid electrolyte will result in a decrease in the conductivity of the solid electrolyte due to the electrolyte interface impedance.
In addition, the improvement of the ionic conductivity is attributed to the lithium-conducting function of the active filler LLZO, and when a plurality of LLZO particles form space charge regions to be connected with each other, a continuous lithium ion transmission channel is formed in the polymer matrix, which is beneficial to improving the transmission rate of lithium ions. The addition of LLZO can also reduce PEO crystallinity. Therefore, if LLZO is omitted, the conductivity is significantly reduced.
As can be seen from a comparison of example 1 and comparative example 7, respectively: substitution of polyethylene oxide for PMMA leads to a decrease in electrochemical performance of the solid-state battery. The reasons may be that: PEO has a stronger ability to dissociate lithium salts, better electrode stability, lower glass transition temperature and interface impedance, and is more suitable for use in the present invention.
As can be seen from a comparison of example 1 and comparative example 8, respectively: an excessive amount of polybenzimidazole may cause a decrease in electrochemical performance of the solid-state battery. The reasons may be that: the strong complexation between the excessive polybenzimidazole and the lithium salt causes the lithium salt to gather, inhibits the uniform distribution of the lithium salt in PEO, and causes the PEO crystallinity to be increased, but can cause the electrochemical performance of the solid-state battery to be reduced.
The above-described embodiments of the present invention have been described in detail, but the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (10)

1. A solid-state battery, characterized in that the solid-state battery comprises a positive electrode sheet, a negative electrode sheet, and a solid electrolyte between the positive electrode sheet and the negative electrode sheet;
the negative electrode sheet comprises a negative electrode solid component, wherein the negative electrode solid component comprises a base material and a coating layer, the base material comprises an oxide and a few-layer MXene, and the coating layer is a carbon coating layer;
the preparation raw materials of the solid electrolyte comprise oxide solid electrolyte, polyoxyethylene, polybenzimidazole and lithium salt; wherein the polybenzimidazole accounts for 2 to 5 percent of the mass of the polyethylene oxide.
2. The solid state battery of claim 1 wherein the oxide in the substrate is selected from the group consisting of Co 3 O 4 、Fe 3 O 4 、GeO 2 、SiO 2 At least one of them.
3. The solid state battery of claim 1 wherein the MXene is selected from the group consisting of Ti 3 C 2 T x 、Ti 2 CT xx 、Nb 3 C 2 T x 、V 2 CT x 、V 3 C 2 T x At least one of them.
4. The solid state battery of claim 1, wherein the oxide solid state electrolyte is selected from at least one of LLZO, LLZTO, LZTO, LLTO.
5. The solid-state battery according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonimide, and lithium bisfluorosulfonyl imide.
6. The solid-state battery according to claim 1, wherein the molar ratio of ethylene oxide of the polyethylene oxide to lithium ions in the lithium salt is 15 to 20:1.
7. the solid state battery of claim 1, wherein the mass ratio of the oxide solid state electrolyte to polyethylene oxide is 1:1.5 to 5.
8. The solid state battery of claim 1, wherein the positive electrode sheet comprises a positive electrode active material selected from LiCoO 2 、LiMn 2 O 4 、LiFePO 4 、LiMnPO 4 、LiVPO 4 At least one of them.
9. A method for producing a solid-state battery according to any one of claims 1 to 8, characterized by being assembled from the positive electrode sheet, solid electrolyte, and negative electrode sheet.
10. Use of a solid-state battery according to any of claims 1-8 in an energy storage device.
CN202311430249.1A 2023-10-31 2023-10-31 Solid-state battery and preparation method and application thereof Pending CN117276647A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340761A (en) * 2022-07-08 2022-11-15 西安电子科技大学 Light PEO/MXene aerogel wave-absorbing material based on polyethylene oxide and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340761A (en) * 2022-07-08 2022-11-15 西安电子科技大学 Light PEO/MXene aerogel wave-absorbing material based on polyethylene oxide and preparation method thereof
CN115340761B (en) * 2022-07-08 2024-06-11 西安电子科技大学 Polyethylene oxide-based light PEO/MXene aerogel wave-absorbing material and preparation method thereof

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