Sulfide-based solid-state lithium-carbon dioxide battery

Abstract

The invention discloses a sulfide-based solid-state lithium-carbon dioxide battery. The sulfide-based solid-state lithium-carbon dioxide battery comprises a positive electrode, a negative electrode, a solid-state electrolyte and an interface protection film, the interface protection film is arranged between the positive electrode and the solid electrolyte; the positive electrode is an integrated positive electrode; the negative electrode is a lithium metal alloy; the solid electrolyte is a sulfide type solid electrolyte; the interface protection film comprises a lithium salt and an ionic liquid. The sulfide-based solid-state lithium-carbon dioxide battery composed of the integrated positive electrode, the sulfide solid-state electrolyte and the lithium metal alloy negative electrode shows relatively low charge-discharge overpotential at room temperature, so that the energy efficiency is improved, the energy loss in the charging process is reduced, and the effects of energy conservation and emission reduction are achieved; and in addition, greenhouse gas carbon dioxide is efficiently utilized, and a novel solid-state secondary battery with high energy density and high safety is expected to be formed.

Description

TECHNICAL FIELD

[0001] The application relates to a sulfide-based solid-state lithium-carbon dioxide battery and belongs to the lithium-carbon dioxide battery field. BACKGROUND

[0002] In recent years, global warming caused by CO2-based greenhouse gases has become increasingly serious, and the greenhouse effect caused thereby brings many hazards. As the latest generation of energy storage batteries, lithium-carbon dioxide batteries have great potential in the carbon dioxide fixation field and are expected to become desirable long-distance power transmission energy storage devices, with a high theoretical energy density (1876 Wh kg -1 ) and a discharge potential (-2.8 V) of CO2 as the positive active material. However, liquid lithium-carbon dioxide batteries cannot meet the requirements of higher energy density, higher safety and longer service life for various application scenarios. Firstly, CO2 diffuses to the negative electrode in the liquid electrolyte, causing serious side reactions of the lithium negative electrode. Secondly, the positive electrode side lacks abundant multi-phase interface structures for the transmission of electrons, lithium ions and gas. Thirdly, the narrow working temperature range of the organic electrolyte causes thermal runaway, and the dendrite growth of the lithium metal negative electrode causes safety problems. SUMMARY

[0003] To overcome the deficiencies of the prior art, the application aims to design a sulfide-based solid-state lithium-carbon dioxide battery, which effectively avoids high overpotential caused by excessive interface resistance and slow CO2 reduction and precipitation kinetics by introducing a sulfide solid-state electrolyte with high lithium ion conductivity and an integrated positive electrode, and can obtain a low charge-discharge overpotential of 0.11 V and 360 cycles of reversible charge-discharge stable cycles.

[0004] According to one aspect of the application, a sulfide-based solid-state lithium-carbon dioxide battery is provided, which comprises a positive electrode, a negative electrode, a solid-state electrolyte, an interface protection film and a battery shell.

[0005] The interface protection film is arranged between the positive electrode and the solid-state electrolyte.

[0006] The positive electrode is an integrated positive electrode.

[0007] The negative electrode is a lithium metal alloy.

[0008] The solid-state electrolyte is a sulfide-type solid-state electrolyte.

[0009] The interface protection film comprises a lithium salt and an ionic liquid.

[0010] The battery shell is arranged on the positive electrode side and is provided with a small hole for introducing CO2 gas.

[0011] Optionally, the sulfide-based solid-state lithium-carbon dioxide battery comprises a lithium metal alloy anode, a solid-state electrolyte, an interface protection film, an integrated cathode, and a solid-state battery test mold.

[0012] Optionally, the solid-state battery test mold has a small hole on the cathode side for the introduction of CO2 gas.

[0013] Optionally, the sulfide-type solid-state electrolyte is selected from at least one of Li6PS5Cl, Li 10 GeP2S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 .

[0014] Optionally, the lithium metal alloy is selected from at least one of lithium-indium alloy, lithium-aluminum alloy, lithium-boron alloy, lithium-silicon alloy.

[0015] Optionally, the lithium salt is selected from at least one of lithium bis-trifluoromethanesulfonimide, lithium tetrafluoroborate.

[0016] Optionally, the ionic liquid is selected from at least one of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate.

[0017] Optionally, the integrated cathode comprises a catalyst, a polymer electrolyte, and a current collector.

[0018] The catalyst comprises a carbon material selected from at least one of carbon nanotubes, graphene, carbon fibers;

[0019] The polymer electrolyte is a complex of lithium salt I and an additive;

[0020] The current collector is selected from at least one of stainless steel mesh, foamed nickel, carbon paper, carbon cloth.

[0021] Optionally, the catalyst further comprises a transition metal element selected from at least one of copper, ruthenium, gold, palladium, platinum.

[0022] Optionally, the loading amount of the transition metal element on the current collector is 0.1-20%.

[0023] Optionally, the lithium salt I is selected from at least one of lithium bis-trifluoromethanesulfonimide, lithium tetrafluoroborate.

[0024] Optionally, the additive is butanedinitrile.

[0025] Optionally, Method I, the preparation method of the integrated cathode material comprises the following steps:

[0026] (1) heat-treating a nitrogen-containing compound and a current collector under an inactive atmosphere, growing in-situ to obtain a current collector containing high-conductive carbon material;

[0027] (2) heating, drying II a mixture of lithium salt I, polymer matrix, stabilizer, solvent I, additive, current collector containing high-conductive carbon material to obtain the integrated positive electrode;

[0028] Optionally, the method for preparing the integrated positive electrode further comprises the following steps:

[0029] S1: heat-treating a nitrogen-containing compound and a current collector under an inactive atmosphere, growing in-situ to obtain a current collector containing high-conductive carbon material;

[0030] S2: soaking the current collector containing high-conductive carbon material in a transition metal salt solution, drying I, annealing under an inactive atmosphere to obtain a current collector containing metal;

[0031] S3: heating, drying II a mixture of lithium salt I, polymer matrix, stabilizer, solvent, additive, current collector containing metal to obtain the integrated positive electrode.

[0032] Optionally, in the step S1, the nitrogen-containing compound is selected from at least one of melamine, urea, dicyandiamide.

[0033] Optionally, the mass ratio of the nitrogen-containing compound and the current collector is (1.0-2.0 g):(0.3-0.5 g).

[0034] Optionally, the heating rate of the in-situ growth is 2-10℃ / min -1 , the temperature of the in-situ growth is 600-800℃, and the time of the in-situ growth is 1-3h.

[0035] Optionally, in the step S2, the transition metal salt in the transition metal salt solution is selected from at least one of copper chloride, ruthenium chloride, gold chloride, palladium chloride, platinum chloride.

[0036] Optionally, the solvent in the transition metal salt solution is ethanol.

[0037] Optionally, the temperature of the drying I is 50-80℃, and the time of the drying I is 6-12h.

[0038] Optionally, the annealing comprises annealing I and annealing II.

[0039] Optionally, the heating rate of the annealing I is 2-10℃ / min -1 , the temperature of the annealing I is 250-350℃, and the time of the annealing I is 2-5h.

[0040] Optionally, the heating rate of annealing II is 1-5℃ / min -1 , the temperature of annealing II is 350-550℃, and the time of annealing II is 2-5h.

[0041] Optionally, in the step S1 and step S2, the non-reactive atmosphere is independently selected from at least one of nitrogen and argon.

[0042] Optionally, in the step S3, the polymer matrix is polyvinylidene fluoride-hexafluoropropylene.

[0043] Optionally, the stabilizer is dibutylhydroxytoluene.

[0044] Optionally, the solvent is dimethyl sulfoxide.

[0045] Optionally, the amount ratio of the polymer matrix, solvent, lithium salt I, stabilizer, and additive is (0.2-0.6g):(2-5mL):(0.1-0.28g):(0.1-0.4g):(0.2-0.7g).

[0046] Optionally, the temperature of drying II is 20-60℃, and the time of drying II is 6-12h.

[0047] Optionally, the method two, the preparation method of the integrated positive electrode comprises the following steps:

[0048] 2.1, after grinding the carbon material and the binder, diluting with the solvent II, coating on the current collector to obtain the current collector coated with the carbon material;

[0049] 2.2, heating and drying II the mixture containing the lithium salt I, the polymer matrix, the stabilizer, the solvent I, the additive, and the current collector coated with the carbon material to obtain the integrated positive electrode.

[0050] Optionally, the preparation method of the integrated positive electrode further comprises the following steps:

[0051] S2.1, soaking the carbon material in a transition metal salt solution, drying III, and annealing under a non-reactive atmosphere to obtain the carbon material containing the transition metal;

[0052] S2.2, after grinding the carbon material containing the transition metal and the binder, diluting with the solvent II, coating on the current collector to obtain the current collector coated with the carbon material containing the transition metal;

[0053] S2.3, heating and drying II the mixture containing the lithium salt I, the polymer matrix, the stabilizer, the solvent I, the additive, and the current collector coated with the carbon material containing the transition metal to obtain the integrated positive electrode material.

[0054] Optionally, in step S2.1, the temperature of drying III is 50-80°C, and the drying time of drying III is 6-12 hours.

[0055] Optionally, in step S2.2, the adhesive is selected from at least one of PVDF and PTFE.

[0056] Optionally, the ratio of the carbon material containing the transition metal to the binder is (7-9):(3-1).

[0057] As an optional implementation, this application is achieved through the following technical solution:

[0058] The integrated cathode material is prepared using two methods: in-situ growth and coating. The specific methods are as follows:

[0059] Method 1: A highly conductive carbon material is grown in situ on the surface of a stainless steel mesh or nickel foam current collector, wherein the carbon-based material is carbon nanotubes; a transition metal catalyst material is prepared, wherein the transition metal is one of copper, ruthenium, gold, palladium, or platinum; and an integrated solid-state lithium-carbon dioxide battery cathode is prepared by introducing a continuous lithium-ion transport medium in situ on the surface of the current collector.

[0060] Method 2: Coat the surface of a carbon paper or carbon cloth current collector with a highly conductive carbon material, wherein the carbon-based material is graphene, carbon nanotubes, or carbon fibers; prepare a transition metal catalyst material, wherein the transition metal is one of copper, ruthenium, gold, palladium, or platinum; and introduce a continuous lithium-ion transport medium in situ onto the surface of the current collector to prepare an integrated solid-state lithium-carbon dioxide battery cathode.

[0061] Furthermore, method one specifically refers to:

[0062] Step 1.1: Spread melamine evenly on the bottom of the ceramic boat, place a layer of carbon paper in the middle, and place the current collector on top of it; place the loaded ceramic boat in a tube furnace and perform high-temperature heat treatment under N2 or Ar atmosphere.

[0063] Step 1.2: Add the transition metal salt to anhydrous ethanol and ultrasonically stir until a transparent solution is obtained; immerse the current collector with carbon material in the ethanol solution containing the transition metal salt and perform rotary evaporation until the liquid is completely evaporated, then place it in a vacuum drying oven for drying; perform two high-temperature annealing treatments under N2 or Ar atmosphere respectively.

[0064] Step 1.3: First, dissolve polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in anhydrous dimethyl sulfoxide (DMSO) and stir at a certain temperature until PVDF-HFP is completely dissolved. Then, add lithium bis(trifluoromethanesulfonyl)imide and the stabilizer butylated hydroxytoluene (BHT) and continue stirring until dissolved. Finally, add succinate and continue stirring to obtain a homogeneous solution. Cut the current collector prepared in step 2 into a certain size and place it on a custom-made polytetrafluoroethylene (PTFE) mold. Then, pour the homogeneous solution onto the current collector and heat it at a certain temperature in a glove box until the DMSO evaporates. Finally, place it in a vacuum drying oven for drying to obtain an integrated positive electrode.

[0065] Furthermore, the second method specifically includes:

[0066] Step 2.1: Add the transition metal salt to anhydrous ethanol and ultrasonically stir until a transparent solution is obtained; immerse graphene, carbon nanotubes or carbon fibers in an ethanol solution containing the metal salt and perform rotary evaporation until the liquid is completely evaporated, then place them in a vacuum drying oven for drying; subject the dried powder to two high-temperature annealing treatments under N2 or Ar atmosphere.

[0067] Step 2.2: Grind copper-loaded graphene, carbon nanotubes or carbon fibers with binder (PVDF) at a mass ratio of (7-9):(3-1), dilute with nitrogen-methylpyrrolidone (NMP) to prepare a free-flowing ink-like slurry, and uniformly coat it onto carbon paper or carbon cloth.

[0068] Step 2.3: First, dissolve polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in anhydrous DMSO and stir at a certain temperature until PVDF-HFP is completely dissolved. Then, add lithium bis(trifluoromethanesulfonyl)imide and stabilizer BHT, and continue stirring until dissolved. Finally, add succinate and continue stirring to obtain a homogeneous solution. Cut the current collector prepared in Step 2.2 into a certain size and place it on a custom PTFE mold. Then, pour the homogeneous solution onto the current collector and heat it at a certain temperature in a glove box until the DMSO evaporates. Finally, place it in a vacuum drying oven for drying to obtain an integrated positive electrode.

[0069] This application discloses a sulfide-based solid-state lithium-carbon dioxide battery. The battery includes a lithium metal alloy negative electrode, a solid electrolyte, an interface protective film, an integrated positive electrode, and a solid-state battery testing mold. The positive electrode is a stainless steel mesh, nickel foam, carbon paper, or carbon cloth made of carbon-supported transition metal material; the negative electrode is a lithium metal alloy; the electrolyte is a sulfide-based solid electrolyte; the battery casing consists of a customized sulfide solid-state battery mold with side wall openings and a closed cavity. The sulfide-based solid-state lithium-carbon dioxide battery, composed of a self-supporting positive electrode, a sulfide solid electrolyte, and a lithium metal alloy negative electrode, exhibits a low charge / discharge overpotential at room temperature, thereby improving energy efficiency, reducing energy loss during charging, and achieving energy saving and emission reduction effects. Furthermore, it efficiently utilizes the greenhouse gas carbon dioxide, and is expected to become a new type of solid-state rechargeable battery with high energy density and high safety.

[0070] The beneficial effects that this application can produce include:

[0071] This application provides a sulfide-based solid-state lithium-carbon dioxide battery. By introducing a sulfide solid electrolyte with high lithium-ion conductivity and an integrated positive electrode, it effectively avoids high overpotentials caused by excessive interface resistance and slow CO2 reduction and precipitation kinetics, achieving a low charge-discharge overpotential of 0.11V and 360 reversible charge-discharge stable cycles. This sulfide-based solid-state lithium-carbon dioxide battery and its integrated positive electrode can efficiently utilize the greenhouse gas CO2, and are expected to become a new type of solid-state rechargeable battery with high energy density and high safety. Attached Figure Description

[0072] Figure 1 This is a schematic diagram of the structure of a sulfide solid lithium-carbon dioxide battery according to this application;

[0073] Figure 2 This is a scanning electron microscope cross-sectional image of the integrated positive electrode synthesized in Example 1 of this application, with a scale bar of 20.0 μm;

[0074] Figure 3 The constant capacity charge-discharge curve of the sulfide-based solid lithium-carbon dioxide battery constructed in Example 1 of this application;

[0075] Figure 4 The constant capacity charge-discharge cycle curve of the sulfide-based solid lithium-carbon dioxide battery constructed in Example 1 of this application;

[0076] Figure 5 The X-ray diffraction pattern of the sulfide solid electrolyte Li6PS5Cl synthesized in Example 1 of this application is shown. Detailed Implementation

[0077] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0078] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0079] The battery performance of this application was tested using constant current charge-discharge technology in a LAND CT2001A system; the phase composition and crystallinity of the samples were analyzed by XRD using a SmartLab instrument with Cu target Kα rays. The scanning speed is 10°min. -1 The samples were characterized using instruments and equipment; the morphological characteristics of the samples were observed using SEM, with the Quanta 200F instrument used.

[0080] like Figure 1 As shown, the sulfide-based solid-state lithium-carbon dioxide battery of the present invention includes a lithium metal alloy negative electrode, a solid electrolyte, an interface protective film, an integrated positive electrode, and a battery casing. The solid electrolyte divides the entire battery into a positive electrode side and a negative electrode side. The positive electrode is a stainless steel mesh, nickel foam, carbon paper, or carbon cloth covered with a carbon-supported transition metal material; the negative electrode is a lithium metal alloy; the electrolyte is a sulfide-based solid electrolyte; the battery casing consists of a customized sulfide solid-state battery mold with sidewall openings and a closed cavity, the closed cavity being equipped with a pressure gauge. The transition metal is one of copper, ruthenium, gold, palladium, or platinum, further introducing a continuous lithium-ion transport medium in situ. The energy storage mechanism of the sulfide-based solid lithium-carbon dioxide battery of the present invention is as follows: During discharge, lithium ions and electrons are dissociated from the lithium metal alloy negative electrode. The lithium ions migrate to the positive electrode through the solid electrolyte, and the electrons reach the positive electrode through the external circuit. On the surface of the positive electrode, lithium ions, electrons and carbon dioxide entering the system from the positive electrode react to generate lithium carbonate and carbon. During charging, lithium carbonate and carbon are reduced to carbon dioxide, lithium ions and electrons through catalysis. The carbon dioxide leaves the system through the positive electrode, and the lithium ions reach the negative electrode through the electrolyte and combine with the electrons that reach the negative electrode through the external circuit to generate lithium metal.

[0081] Overall battery reaction:

[0082] Battery assembly: The prepared integrated positive electrode is rapidly transferred to a glove box filled with Ar gas (H2O ≤ 0.01 ppm, O2 ≤ 0.01 ppm). The negative electrode uses a lithium indium alloy sheet (circular with a diameter of 10 mm). The solid electrolyte is a sulfide-type solid electrolyte. A conductive Li-1 layer is coated between the solid electrolyte and the positive electrode. +The electrolyte is specifically one of either a 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide solution dissolving lithium bis(trifluoromethanesulfonyl)imide or a 1-ethyl-3-methylimidazolium tetrafluoroborate solution dissolving lithium tetrafluoroborate. After battery assembly, the battery is placed in an air battery test mold, removed from the glove box, and CO2 gas is introduced to purge the Ar in the bottle, placing the battery in a CO2-filled atmosphere. Then, it is placed in a constant temperature chamber at 25±2℃ for 12 hours to allow the battery to reach a stable state before electrochemical performance testing.

[0083] The specific process for preparing the integrated positive electrode in this sulfide-based solid lithium-carbon dioxide battery energy storage device is as follows:

[0084] Method 1: A highly conductive carbon material is grown in situ on the surface of a stainless steel mesh current collector, wherein the carbon-based material is carbon nanotubes; a transition metal catalyst material is prepared, wherein the transition metal is one of copper, ruthenium, gold, palladium, or platinum; and an integrated solid-state lithium-carbon dioxide battery cathode is prepared by introducing a continuous lithium-ion transport medium in situ on the surface of the current collector.

[0085] Step 1.1: Spread melamine evenly on the bottom of the ceramic boat, place a layer of carbon paper in the middle, and place the current collector on top of it; place the loaded ceramic boat in a tube furnace and perform high-temperature heat treatment under N2 or Ar atmosphere.

[0086] Step 1.2: Add the metal salt to anhydrous ethanol and ultrasonically stir until a transparent solution is obtained; immerse the current collector with carbon material in the ethanol solution containing the metal salt and perform rotary evaporation until the liquid is completely evaporated, then place it in a vacuum drying oven for drying; perform two high-temperature annealing treatments under N2 or Ar atmosphere respectively.

[0087] Step 1.3: First, dissolve PVDF-HFP in anhydrous DMSO and stir at a certain temperature until PVDF-HFP is completely dissolved. Then, add lithium bis(trifluoromethanesulfonyl)imide and stabilizer BHT, and continue stirring until dissolved. Finally, add succinate and continue stirring to obtain a homogeneous solution. Cut the current collector prepared in Step 1.2 into a certain size and place it on a custom-made PTFE mold. Then, pour the homogeneous solution onto the current collector and heat it at a certain temperature in a glove box until the DMSO evaporates. Finally, place it in a vacuum drying oven for drying to obtain an integrated positive electrode.

[0088] Method 2: Coat the surface of a carbon paper or carbon cloth current collector with a highly conductive carbon material, wherein the carbon-based material is graphene or carbon fiber; prepare a transition metal catalyst material, wherein the transition metal is one of copper, ruthenium, gold, palladium, or platinum; and introduce a continuous lithium-ion transport medium in situ onto the surface of the current collector to prepare an integrated solid-state lithium-carbon dioxide battery cathode.

[0089] Step 2.1: Add the metal salt to anhydrous ethanol and ultrasonically stir until a transparent solution is obtained; immerse the graphene or carbon fiber material in the ethanol solution containing the metal salt and perform rotary evaporation until the liquid is completely evaporated, then place it in a vacuum drying oven for drying; subject the dried powder to two high-temperature annealing treatments under N2 or Ar atmosphere.

[0090] Step 2.2: Grind the metal-loaded graphene or carbon nanotubes with PVDF at a mass ratio of (7-9):(3-1), dilute with NMP to prepare a free-flowing ink-like slurry, and uniformly coat it onto carbon paper or carbon cloth.

[0091] Step 2.3: First, dissolve PVDF-HFP in anhydrous DMSO and stir at a certain temperature until PVDF-HFP is completely dissolved. Then, add lithium bis(trifluoromethanesulfonyl)imide and stabilizer BHT, and continue stirring until dissolved. Finally, add succinate and continue stirring to obtain a homogeneous solution. Cut the current collector prepared in Step 2.2 into a certain size and place it on a custom PTFE mold. Then, pour the homogeneous solution onto the current collector and heat it at a certain temperature in a glove box until the DMSO evaporates. Finally, place it in a vacuum drying oven for drying to obtain an integrated positive electrode.

[0092] The following is a detailed description of a specific data example:

[0093] Example 1

[0094] (1) Take a stainless steel mesh current collector slice with a size of 3*6cm, and then use acetone, ethanol and water to ultrasonically clean it multiple times, each time for at least 10 minutes.

[0095] (2) Spread 1.0g of melamine evenly on the bottom of a ceramic boat, place a layer of carbon paper in the middle, and place a stainless steel mesh current collector on top of it. In an Ar atmosphere, spray at 2℃ for 2 min. -1 The heating rate is increased to 600℃ and held for 1 hour.

[0096] (3) The stainless steel mesh with carbon material grown after annealing was placed in an ethanol solution of anhydrous copper chloride and subjected to rotary evaporation. After the liquid was completely evaporated, it was placed in a vacuum drying oven at 50°C for 6 hours.

[0097] (4) The dried positive electrode sheet was subjected to two high-temperature annealing treatments under an Ar atmosphere. The parameters for the first heat treatment were 2℃ min. -1 The heating rate was increased to 250℃, held for 2 hours, removed, washed with ethanol, and dried in a vacuum drying oven; the second heat treatment parameters were 1℃ / min. -1The heating rate was increased to 350℃ and held for 2 hours. The metal loading on the carbon nanotubes was 5%.

[0098] (5) The obtained electrode material is introduced in situ into the succinate-based solid electrolyte under an Ar atmosphere to form a continuous lithium-ion transport layer. First, 0.2 g of PVDF-HFP is dissolved in 2 mL of anhydrous DMSO and stirred at 50 °C until PVDF-HFP is completely dissolved. Then, 0.1 g of lithium bis(trifluoromethanesulfonylimide) and 0.1 g of stabilizer BHT are added and stirred until dissolved. Finally, 0.2 g of succinate is added and stirred to obtain a uniform solution. The uniform solution is then poured onto the electrode material prepared in step (4), heated to 20 °C in a glove box, and dried for 36 h until DMSO evaporates. Finally, it is placed in a vacuum drying oven and dried at 20 °C for 36 h to obtain an integrated positive electrode.

[0099] (6) Battery assembly: First, Li6PS5Cl sulfide powder is pressed into a cylindrical shape in a mold, and then positive and negative electrodes are placed on both sides respectively. The integrated positive electrode and the lithium indium metal alloy (LiIn) are used as positive and negative electrodes respectively. A 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide protective film containing lithium bis(trifluoromethanesulfonyl)imide is coated between the positive electrode and the solid electrolyte. The battery is tested in a customized solid battery mold.

[0100] Figure 1 This is a schematic diagram of the structure of the sulfide-based solid-state lithium-carbon dioxide battery in Example 1; Figure 2 The image shown is a cross-sectional scanning electron microscope image of the integrated positive electrode synthesized in Example 1. It can be seen that a layer of succinic acid-based solid electrolyte is uniformly coated on the surface of the copper-loaded carbon nanotubes.

[0101] Battery performance was tested using constant current charge-discharge technology in a LAND CT2001A system at a current density of 500 mA g. -1 Fixed capacity 1000mAh g -1 The charge / discharge cutoff potential is 2.3–4.6V. Figure 3 The charge-discharge curves of the solid-state lithium-carbon dioxide battery constructed in Example 1 are shown, with charge and discharge potentials of 1.77V and 1.66V, respectively. Figure 4 The charge-discharge cycle curves of the sulfide-based solid lithium-carbon dioxide battery constructed in Example 1 show that the battery with the copper catalyst can cycle reversibly for 360 cycles. Figure 5 The X-ray diffraction pattern of the sulfide solid electrolyte Li6PS5Cl synthesized in Example 1 is shown below. Figure 5 This demonstrates the successful preparation of Li6PS5Cl.

[0102] Example 2

[0103] (1) Take a piece of nickel foam current collector with a size of 3*6cm, and then use acetone, ethanol and water to ultrasonically clean it multiple times, each time for at least 10 minutes.

[0104] (2) Spread 2.0g of melamine evenly on the bottom of a ceramic boat, place a layer of carbon paper in the middle, and place a foamed nickel current collector on top of it. In an Ar atmosphere, incubate at 5℃ for 1 minute. -1 The heating rate was increased to 750℃ and held for 2 hours.

[0105] (3) The above-mentioned annealed nickel foam with carbon material was placed in an ethanol solution of anhydrous copper chloride and subjected to rotary evaporation treatment until the liquid was completely evaporated. Then, it was placed in a vacuum drying oven at 60°C for 8 hours of drying.

[0106] (4) The dried positive electrode sheet was subjected to two high-temperature annealing treatments under N2 atmosphere. The parameters for the first heat treatment were 5℃ min. -1 The heating rate was increased to 350℃, held for 5 hours, removed, washed with ethanol, and dried in a vacuum drying oven; the second heat treatment parameters were 2℃ / min. -1 The temperature was increased to 500℃ and held for 5 hours. The metal loading on the carbon nanotubes was 0.1%.

[0107] (5) The obtained electrode material is introduced in situ into a succinic acid-based solid electrolyte under a N2 atmosphere to form a continuous lithium-ion transport layer. First, 0.3 g of PVDF-HFP is dissolved in 3 mL of anhydrous DMSO and stirred at 60 °C until PVDF-HFP is completely dissolved. Then, 0.16 g of lithium bis(trifluoromethanesulfonylimide) and 0.2 g of stabilizer BHT are added and stirred until dissolved. Finally, 0.3 g of succinic acid is added and stirred to obtain a uniform solution. The uniform solution is then poured onto the electrode material prepared in step (4), heated to 30 °C in a glove box, and dried for 50 h until DMSO evaporates. Finally, it is placed in a vacuum drying oven and dried at 30 °C for 50 h to obtain an integrated positive electrode.

[0108] (6) Battery assembly: First, Li 10 GeP2S 12 The sulfide powder is pressed into a cylindrical shape in a mold, and then positive and negative electrodes are placed on both sides respectively. The integrated positive electrode and the lithium aluminum alloy serve as the positive and negative electrodes respectively. A protective film of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide containing lithium bis(trifluoromethanesulfonyl)imide is coated between the positive electrode and the solid electrolyte. The test is conducted in a customized solid-state battery mold.

[0109] Example 3

[0110] (1) Chlorides of ruthenium, gold, palladium, and platinum were added to anhydrous ethanol and ultrasonically stirred until a transparent solution was obtained. Graphene carbon material was immersed in the above ethanol solution and subjected to rotary evaporation until the liquid was completely evaporated. Then, it was placed in a vacuum drying oven at 70℃ for 10 hours. The dried powder was then subjected to two high-temperature annealing treatments under N2 atmosphere. The parameters for the first heat treatment were 10℃ / min. -1 The heating rate was increased to 350℃, held for 5 hours, then removed, washed with ethanol, and dried in a vacuum drying oven; the second heat treatment parameters were 5℃ / min. -1 The temperature was increased to 550℃ and held for 5 hours. The metal loading on the graphene was 20%.

[0111] (2) The metal-loaded graphene and PVDF were ground at a mass ratio of 9:1 and diluted with NMP to form a fluid ink-like slurry, which was then uniformly coated onto carbon paper.

[0112] (3) The obtained electrode material was introduced in situ into a succinic acid-based solid electrolyte under a N2 atmosphere to form a continuous lithium-ion transport layer. First, 0.6 g of PVDF-HFP was dissolved in 5 mL of anhydrous DMSO and stirred at 80 °C until PVDF-HFP was completely dissolved. Then, 0.28 g of lithium bis(trifluoromethanesulfonylimide) and 0.4 g of stabilizer BHT were added and stirred until dissolved. Finally, 0.7 g of succinic acid was added and stirred to obtain a uniform solution. The uniform solution was then poured onto the electrode material prepared in step (2), heated to 60 °C in a glove box, and dried for 60 h until DMSO evaporated. Finally, it was placed in a vacuum drying oven and dried at 60 °C for 60 h to obtain an integrated positive electrode.

[0113] (4) Battery assembly: First, Li 9.54 Si 1.74 P 1.44 S 11.7 C l0.3 The sulfide powder is pressed into a cylindrical shape in a mold, and then positive and negative electrodes are placed on both sides respectively. The integrated positive electrode and the lithium boron alloy serve as the positive and negative electrodes respectively. A protective film of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide containing lithium bis(trifluoromethanesulfonyl)imide is coated between the positive electrode and the solid electrolyte. The test is conducted in a customized solid-state battery mold.

[0114] Example 4

[0115] (1) Carbon fiber and PVDF were ground at a mass ratio of 7:3 and diluted with NMP to prepare a free-flowing, ink-like slurry, which was then uniformly coated onto carbon cloth. The metal loading on the carbon fiber was 0%.

[0116] (2) The obtained electrode material was introduced in situ into a succinic acid-based solid electrolyte under an Ar atmosphere to form a continuous lithium-ion transport layer. First, 0.2 g of PVDF-HFP was dissolved in 2 mL of anhydrous DMSO and stirred at 50 °C until PVDF-HFP was completely dissolved. Then, 0.1 g of lithium bis(trifluoromethanesulfonylimide) and 0.1 g of stabilizer BHT were added and stirred until dissolved. Finally, 0.2 g of succinic acid was added and stirred to obtain a uniform solution. The uniform solution was then poured onto the electrode material prepared in step (1) and heated to 60 °C in a glove box for 48 h to dry until DMSO evaporated. Finally, it was placed in a vacuum drying oven and dried at 50 °C for 48 h to obtain an integrated positive electrode.

[0117] (3) Battery assembly: First, Li6PS5Cl sulfide powder is pressed into a cylindrical shape in a mold, and then positive and negative electrodes are placed on both sides respectively. The integrated positive electrode and lithium silicon alloy are used as positive and negative electrodes respectively. A protective film of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide containing lithium bis(trifluoromethanesulfonyl)imide is coated between the positive electrode and the solid electrolyte. The battery is tested in a customized solid battery mold.

[0118] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. A sulfide-based solid-state lithium-carbon dioxide battery, characterized in that, The sulfide-based solid lithium-carbon dioxide battery includes a positive electrode, a negative electrode, a solid electrolyte, an interface protective film, and a battery casing. The interface protective film is provided between the positive electrode and the solid electrolyte; The positive electrode is an integrated positive electrode; The negative electrode is a lithium metal alloy; The solid electrolyte is a sulfide-type solid electrolyte; The interface protective film comprises lithium salt and ionic liquid; The battery casing is located on the positive electrode side and has a small hole for introducing CO2 gas.

2. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 1, characterized in that, The sulfide-type solid electrolyte is selected from Li6PS5Cl, Li 10 GeP2S 12 Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 At least one of them; Preferably, the lithium metal alloy is selected from at least one of lithium indium alloy, lithium aluminum alloy, lithium boron alloy, and lithium silicon alloy; Preferably, the lithium salt is selected from at least one of lithium bis(trifluoromethanesulfonyl)imide and lithium tetrafluoroborate; Preferably, the ionic liquid is selected from at least one of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and 1-ethyl-3-methylimidazolium tetrafluoroboric acid.

3. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 1, characterized in that, The integrated positive electrode includes a catalyst, a polymer electrolyte, and a current collector; The catalyst includes a carbon material, which is selected from at least one of carbon nanotubes, graphene, and carbon fibers. The polymer electrolyte is a composite of lithium salt I and additives; The current collector is selected from at least one of stainless steel mesh, nickel foam, carbon paper, and carbon cloth.

4. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 3, characterized in that, The catalyst further includes a transition metal element, which is selected from at least one of copper, ruthenium, gold, palladium, and platinum; Preferably, the loading of the transition metal element on the current collector is 0.1% to 20%; Preferably, the lithium salt I is selected from at least one of lithium bis(trifluoromethanesulfonyl)imide and lithium tetrafluoroborate; Preferably, the additive is succinic anhydride.

5. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 3, characterized in that, Method 1, the preparation method of the integrated positive electrode includes the following steps: (1) Under an inactive atmosphere, nitrogen-containing compounds and current collectors are heat-treated and grown in situ to obtain current collectors containing highly conductive carbon materials. (2) A mixture of lithium salt I, polymer matrix, stabilizer, solvent I, additive, and current collector containing highly conductive carbon material is heated and dried II to obtain the integrated positive electrode; Preferably, the method for preparing the integrated positive electrode further includes the following steps: S1: Under an inactive atmosphere, nitrogen-containing compounds and current collectors are heat-treated and grown in situ to obtain current collectors containing highly conductive carbon materials. S2: Immerse the current collector containing highly conductive carbon material in a transition metal salt solution, dry it, and anneal it under an inactive atmosphere to obtain a current collector containing metal. S3: A mixture of lithium salt I, polymer matrix, stabilizer, solvent, additive, and metal-containing current collector is heated and dried II to obtain the integrated positive electrode.

6. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 5, characterized in that, In step S1, the nitrogen-containing compound is selected from at least one of melamine, urea, and dicyandiamide; Preferably, the mass ratio of the nitrogen-containing compound to the current collector is (1.0–2.0 g): (0.3–0.5 g); Preferably, the heating rate for the in-situ growth is 2–10 °C / min. -1 The in-situ growth temperature is 600–800℃, and the in-situ growth time is 1–3 hours; Preferably, in step S2, the transition metal salt in the transition metal salt solution is selected from at least one of copper chloride, ruthenium chloride, gold chloride, palladium chloride, and platinum chloride; Preferably, the solvent in the transition metal salt solution is ethanol; Preferably, the temperature of drying I is 50-80°C, and the drying time is 6-12 hours; Preferably, the annealing includes annealing I and annealing II; Preferably, the heating rate of annealing I is 2–10 °C / min. -1 The annealing temperature for I is 250–350℃, and the annealing time for I is 2–5 hours. Preferably, the heating rate of annealing II is 1–5 °C / min. -1 Annealing II is performed at a temperature of 350–550℃ for 2–5 hours. Preferably, in steps S1 and S2, the inactive atmosphere is independently selected from at least one of nitrogen and argon.

7. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 5, characterized in that, In step S3, the polymer matrix is ​​polyvinylidene fluoride-hexafluoropropylene; Preferably, the stabilizer is butylated hydroxytoluene; Preferably, the solvent is dimethyl sulfoxide; Preferably, the ratio of the polymer matrix, solvent, lithium salt I, stabilizer, and additive is: (0.2-0.6g): (2-5mL): (0.1-0.28g): (0.1-0.4g): (0.2-0.7g); Preferably, the temperature of the drying II process is 20–60°C, and the drying time is 36–60 h.

8. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 3, characterized in that, Method 2, the preparation method of the integrated positive electrode includes the following steps: 2.1 After grinding the carbon material and binder, dilute it with solvent II and coat it onto the current collector to obtain a current collector coated with carbon material; 2.2 A mixture containing lithium salt I, polymer matrix, stabilizer, solvent I, additives, and current collector coated with carbon material is heated and dried II to obtain the integrated positive electrode.

9. The sulfide-based solid titanium lithium-carbon dioxide battery according to claim 8, characterized in that, The method for preparing the integrated positive electrode further includes the following steps: S2.

1. Immerse the carbon material in a transition metal salt solution, dry it (III), and anneal it under an inactive atmosphere to obtain a carbon material containing a transition metal. S2.2 After grinding the carbon material containing the transition metal with the binder, it is diluted with solvent II and coated onto the current collector to obtain a current collector coated with the carbon material of the transition metal. S2.

3. A mixture containing lithium salt I, polymer matrix, stabilizer, solvent I, additives, and carbon material coated with transition metal is heated and dried II to obtain the integrated cathode material.

10. The sulfide-based solid-state lithium-carbon dioxide battery according to claim 9, characterized in that, In step S2.1, the temperature of drying III is 50-80°C, and the drying time of drying III is 6-12 hours. Preferably, in step S2.2, the adhesive is selected from at least one of PVDF and PTFE; Preferably, the ratio of the carbon material containing the transition metal to the binder is (7-9):(3-1).

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