CN115566251A - Flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and preparation method thereof - Google Patents
Flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and preparation method thereof Download PDFInfo
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
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Abstract
The invention claims a flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and a preparation method thereof, and the preparation method specifically comprises the following steps: 1. designing a flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at room temperature (0-30 ℃), low temperature (-60-0 ℃) and ultralow temperature (-60 ℃), preparing a flexible optical window to realize flexible and totally-enclosed battery packaging and light transmission higher than 90%, and using a flexible metal-semiconductor micro-nano structure photo-thermal current collector as a negative current collector of the battery, a flexible metal lithium negative electrode, a flexible polymer solid electrolyte and a flexible carbon-sulfur composite positive electrode; 2. the flexible photo-thermal current collector is prepared by the photo-thermal effect of the metal plasma and the light trapping effect of the semiconductor three-dimensional nano structure, so that efficient light absorption and all-around photo-thermal conversion in a full spectrum range are realized, and the working performances of the polymer all-solid-state lithium-sulfur battery at room temperature (0-30 ℃), low temperature (-60-0 ℃) and ultralow temperature (< -60 ℃) are improved.
Description
Technical Field
The invention belongs to the technical field of photo-thermal batteries, and particularly belongs to a flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and a preparation method thereof.
Background
Solid-state lithium ion batteries using solid electrolyte (SSE) instead of liquid electrolyte are hot spots for the next generation of high energy density energy storage systems due to their advantages of high safety, high energy density, etc. Besides high safety and high energy density, further expanding the working temperature range of the lithium ion battery to expand the application field of the lithium ion battery also becomes a main challenge facing the current research. For example, commercial/military grade batteries are expected to operate at temperatures between-30 ℃ and 60 ℃. These low temperature challenges limit the application of lithium ion batteries in severe conditions such as cold mountainous areas, deep sea, and aerospace, particularly aerospace-grade batteries, which typically need to withstand operating temperatures of-60 ℃.
Solid state/all solid state lithium sulfur batteries are considered the most potential high specific energy battery system for future applications. The solid electrolyte can effectively inhibit the shuttle effect of polysulfide in the lithium-sulfur battery, and can block lithium dendrite, so that the metal lithium can be used as a negative electrode, and a safe and high-specific energy storage battery with the energy density higher than 500Wh/kg is expected to be realized. These advantages have greatly stimulated the enthusiasm of researchers at home and abroad for studying solid-state lithium-sulfur batteries. The polymer solid electrolyte has potential advantages in the aspect of developing safe and high specific energy lithium ion batteries due to high ionic conductivity and good interface wettability. However, poor ion transport and storage at room temperature or even lower temperatures of polymer electrolytes and their interfaces, resulting in current Polymer (PEO) solid-state lithium metal batteries that can only operate at higher temperatures (50-70 ℃) limits their further applications.
CN109713402A, a solar photo-thermal lithium battery capable of working in an extreme temperature range, comprises a closed lithium ion battery and a semi-open lithium-gas battery. When light is irradiated from the positive electrode side, the photothermal positive electrode can capture sunlight and convert the sunlight into heat to increase the internal temperature of the entire battery assembly, so that the battery assembly can operate in an extremely low temperature environment; when light irradiates from one side of the negative electrode, the photo-thermal negative current collector absorbs sunlight and converts the sunlight into heat which is transferred to the electrolyte and the positive electrode through the negative electrode, so that the whole battery assembly is heated, and the battery assembly works in a very low temperature environment. The extremely low temperature environment temperature is more than or equal to-200 ℃.
The semi-open lithium-gas battery system described in patent CN109713402a has the following drawbacks: (1) the solar photo-thermal all-solid-state lithium-air battery based on an inorganic solid electrolyte system with high mechanical strength such as LAGP (LAGP-lead) is difficult to be practically applied due to a semi-open battery system; (2) the volume and mass of the battery are large and the energy density is difficult to be improved due to an inorganic solid electrolyte system with high mechanical strength such as LAGP (lead-free lead phosphate); (3) the inorganic solid electrolyte system based on LAGP and other high mechanical strength can not realize the functions of flexible batteries such as bending and folding, so that the application field is limited. The closed lithium ion battery system of the patent has the following defects: (4) the specific battery packaging process and the design and preparation of the optical window layer are not involved; (5) the irradiation light source is limited to sunlight and to the vertical incidence of sunlight, so that the application is limited; (6) the negative photo-thermal current collector is formed by combining an independent photo-thermal material and a negative current collector instead of an integrated design, so that the size and the mass of the battery are large, and the energy density is difficult to improve; (7) the lithium-sulfur battery positive electrode is formed by compounding 5-85% of sulfur active matter, 3-50% of conductive agent and 3-15% of binder by mass percent, and the problems of poor conductivity, low active matter load, large volume expansion and the like of the battery positive electrode easily occur.
The invention relates to a totally-enclosed photo-thermal lithium-sulfur battery system, which effectively overcomes the defects (1) of the CN 109713402A; the invention relates to a soft package battery system based on an integrated ultrathin photothermal current collector, ultrathin solid electrolyte, an ultrathin metal lithium cathode and a carbon-sulfur composite anode, which has small volume and light weight and effectively overcomes the defects (2) and (6) of CN 109713402A; the invention relates to a flexible all-solid-state photo-thermal battery system which effectively overcomes the defect (3) of CN 109713402A; the invention relates to a specific battery packaging process and design and preparation of an optical window layer, provides a physical image of a packaged flexible all-solid-state photo-thermal lithium-sulfur battery and working performance data thereof in the environment of room temperature (30 ℃) and low temperature (-60 ℃), and effectively overcomes the defect (4) of the patent CN 109713402A; the flexible photo-thermal current collector disclosed by the invention can realize high-efficiency light absorption (the light absorption rate is higher than 90% in the wavelength range of 200-2500 nm) in a full spectrum range and omnibearing photo-thermal conversion, and effectively overcomes the defect (5) of CN 109713402A; the flexible lithium-sulfur battery positive electrode disclosed by the invention is prepared by repeatedly sintering and grinding carbon (Ketjen black, carbon nano tubes and the like) and sulfur, and the high conductivity and unique structure of the carbon (Ketjen black, carbon nano tubes and the like) material can effectively improve the conductivity of the sulfur positive electrode, improve the loading capacity of sulfur, relieve volume expansion and effectively overcome the defect (7) of the patent CN 109713402A;
disclosure of Invention
The present invention is directed to solving the above problems of the prior art. A flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature and a preparation method thereof are provided. The technical scheme of the invention is as follows:
a flexible all-solid-state photothermal lithium sulfur cell operable at low temperatures comprising:
the flexible optical window, the flexible photo-thermal current collector, the flexible metal lithium cathode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite anode are sequentially arranged from top to bottom. The flexible optical window realizes flexible and totally-enclosed battery packaging, realizes light transmission higher than 90%, the flexible photo-thermal current collector combines the metal plasma photo-thermal effect and the light trapping effect of a semiconductor three-dimensional nanostructure to realize efficient light absorption and omnibearing photo-thermal conversion in a full spectrum range, provides heat for the flexible all-solid-state lithium-sulfur battery based on the polymer all-solid electrolyte in room temperature, low temperature and ultralow temperature environments, the flexible metal lithium cathode is the cathode of the flexible all-solid-state lithium-sulfur battery based on the polymer all-solid electrolyte and is used for providing lithium ions, the flexible polymer solid electrolyte is used for transmitting the lithium ions between the anode and the cathode of the battery, the interface wettability between the electrolyte and the anode is enhanced to improve the working performance of the battery, the carbon and the composite of the flexible carbon and sulfur composite anode improves the conductive performance of an active substance sulfur, and relieves the volume expansion of the sulfur anode in the charging and discharging process.
Furthermore, the flexible optical window, the flexible photo-thermal current collector, the flexible metal lithium cathode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite anode adopt a soft package totally-enclosed packaging process based on an aluminum plastic film.
Further, the flexible optical window is a high-light-transmission flexible film such as PET/PI/PC (polyethylene terephthalate/polyimide/polycarbonate), and the flexible photo-thermal current collector is of a metal-semiconductor micro-nano composite structure, a metal nano particle structure and a metal nano wire structure; the metal lithium cathode is a thinned lithium foil or a sputtered lithium film; the flexible polymer solid electrolyte is a polymer solid electrolyte compounded by PEO, lithium salt and alumina nano particles or a polymer solid electrolyte compounded by PEO and lithium salt; the flexible carbon-sulfur composite positive electrode is a sulfur positive electrode prepared by compounding ketjen black and elemental sulfur, or a sulfur positive electrode prepared by compounding a carbon nano tube and elemental sulfur, or a sulfur positive electrode prepared by compounding graphene and elemental sulfur.
A preparation method of the flexible all-solid-state photo-thermal lithium-sulfur battery comprises the following steps:
preparing a flexible optical window and packaging a battery system;
preparing a flexible photo-thermal current collector;
preparing a flexible metal lithium cathode;
preparing a flexible polymer solid electrolyte;
preparing a flexible carbon-sulfur composite anode;
further, the preparation of the flexible optical window and the packaging of the battery system comprise the following steps: (1) the single side of the aluminum-plastic film is punched (the aperture is not limited and is determined according to the actual anode and cathode of the battery and a current collector), a layer of hot melt adhesive is added between the high-light-transmission flexible film (PET/PI/PC, the light transmittance is more than 90%) and the punched aluminum-plastic film by using a high-temperature hot melting process, and then the aluminum-plastic film is thermally sealed at about 300 ℃ until the aluminum-plastic film is firmly adhered. (2) And sequentially encapsulating the flexible photo-thermal current collector, the flexible metal lithium cathode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite anode in an aluminum plastic film soft package containing a flexible optical window to realize totally enclosed encapsulation. Wherein the photo-thermal current collector faces the high-transmittance flexible optical window layer. (3) Aluminum is used as a positive conductive tab to be packaged at the flexible carbon-sulfur composite positive terminal, and nickel is used as a negative conductive tab to be packaged between the flexible photo-thermal current collector and the flexible metal lithium foil/lithium film.
Further, the preparation steps of the flexible photo-thermal current collector specifically comprise; the preparation method comprises the steps of taking a flexible ultrathin porous metal film with the thickness of 100-0.3 mm as a substrate, growing a metal oxide nanowire on the flexible ultrathin porous metal film by adopting a thermal oxidation process, coating amorphous silicon a-Si or amorphous germanium a-Ge on the flexible ultrathin porous metal film by adopting a semiconductor film preparation process to form a metal oxide/Si (Ge) core-shell structure, and preparing a self-supporting flexible metal-semiconductor micro-nano structure photo-thermal current collector by utilizing high-temperature reduction of the metal oxide and diffusion of metal in a silicon (germanium) shell layer.
Further, the preparation process of the metal oxide-silicon (germanium) core-shell structure comprises Chemical Vapor Deposition (CVD) or plasma chemical vapor deposition (PECVD); the high-temperature reduction of the metal oxide may be performed by a reducing gas such as hydrogen or carbon monoxide, or may be performed by a powder having a reducing property such as carbon powder.
Further, the preparation method of the flexible lithium metal negative electrode specifically comprises the following steps: commercial lithium metal sheets are made into lithium foils with the thickness less than 100um through a thinning process, or lithium metal films with the thickness less than 50um are prepared through a sputtering coating process.
Further, the preparation step of the flexible polymer solid electrolyte comprises the following steps: mixing polyethylene oxide powder PEO and lithium salt LiTFSI according to a certain molar ratio, adding a certain amount of inorganic filler to form mixed powder, adding a certain amount of acetonitrile into the mixed powder, and magnetically stirring for 24 hours to form transparent PEO-based polymer gel. And dripping the obtained PEO-based polymer gel into a mould, standing for 48 hours, and forming a film to form the PEO-based polymer solid electrolyte film.
Further, the preparation method of the flexible carbon-sulfur composite positive electrode specifically comprises the following steps: mixing a certain amount of carbon powder with elemental sulfur (sublimed sulfur) powder, and grinding for 2 hours to form carbon-sulfur mixed powder; annealing the formed carbon-sulfur mixed powder at 140-160 ℃ in an argon atmosphere (3-5 hours) to form carbon-sulfur composite positive electrode powder; then, grinding the carbon-sulfur composite positive electrode powder for 1 hour again, and then annealing at 180-220 ℃ (1-2 hours) to form a final carbon-sulfur composite positive electrode (powder); adding a certain amount of PVDF gel and NMP solution into the carbon-sulfur composite positive electrode (powder), uniformly stirring to form a carbon-sulfur positive electrode coating, uniformly coating the carbon-sulfur positive electrode coating on the surface of an aluminum foil or a carbon cloth by using a coating process, and drying at 40 ℃ to form a film.
The invention has the following advantages and beneficial effects:
the flexible all-solid-state photo-thermal lithium-sulfur battery system capable of working at low temperature is unique. The method comprises a totally-enclosed soft package packaging process based on a flexible optical window layer (PET, PI and PC) and an aluminum plastic film, a flexible photo-thermal current collector capable of absorbing incident light in a wide spectrum and all-round mode, a flexible polymer solid electrolyte with high interface wettability and ionic conductivity, a flexible carbon-sulfur composite anode with high active load and low volume expansion and a flexible metal lithium cathode prepared through a thinning process, a sputtering coating process and the like. The flexible all-solid-state photo-thermal lithium-sulfur battery can realize high safety and high energy density, and can work in the environment of room temperature (0 ℃ to 30 ℃), low temperature (-60 ℃ to 0 ℃) and ultralow temperature (-60 ℃); the wearable intelligent control system can be applied to the fields of aerospace, satellite detection, intelligent wearing and extreme working environments.
The flexible optical window layer (PET, PI, PC) based soft-pack packaging design is unique. The soft package based on the flexible optical window (PET, PI, PC) and the aluminum plastic film, which is designed by adopting a high-temperature hot melting process, not only ensures the good sealing performance of the flexible photo-thermal lithium-sulfur battery, but also can realize efficient light absorption through the high-light-transmission flexible optical window by the photo-thermal current collector in the battery.
And (II) the design and preparation process of the flexible metal-semiconductor micro-nano structure photo-thermal current collector are unique. The photo-thermal current collector is mainly prepared by combining a thermal oxidation process, a plasma chemical vapor deposition process and a high-temperature reduction process. On one hand, the metal plasma photothermal effect and the light trapping effect of the semiconductor three-dimensional nanostructure are effectively combined to realize high-efficiency light absorption (more than 90%) and photothermal conversion in all directions in a full spectrum range, so that incident light from all directions is efficiently captured and rapidly converted into heat, direct and rapid continuous heat supply is provided for a lithium anode, an electrolyte, a cathode and the whole battery, charge is efficiently stored and transmitted in an electrolyte/electrode material, and the flexible all-solid photothermal lithium-sulfur battery can work at room temperature and low temperature. On the other hand, the metal-semiconductor micro-nano structure shell layer semiconductor material can form an alloy layer (such as a lithium silicon alloy layer) with metal lithium in the charging and discharging process, so that the cycle life of the battery is prolonged.
Drawings
Fig. 1 is a schematic structural view of a flexible all-solid-state photothermal lithium-sulfur battery provided by the present invention;
fig. 2 is a light absorption curve of a flexible all-solid-state photothermal lithium sulfur battery negative copper silicon micro-nano structure photothermal current collector provided in a preferred embodiment of the present invention;
FIG. 3 is a graph showing the internal temperature of a flexible all-solid photothermal lithium sulfur battery according to a preferred embodiment of the present invention as a function of illumination intensity and time;
FIG. 4 shows the room temperature and low temperature charging and discharging curves of a flexible all-solid photo-thermal lithium-sulfur battery according to a preferred embodiment of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail and clearly with reference to the accompanying drawings. The described embodiments are only some of the embodiments of the present invention.
The technical scheme for solving the technical problems is as follows:
the invention provides a design and a preparation method of a novel flexible all-solid-state photo-thermal lithium-sulfur battery. The schematic diagram of the battery structure is shown in FIG. 1, which is from top to bottom
The device comprises a flexible optical window 1, a flexible photo-thermal current collector 2 of a metal-semiconductor micro-nano structure, a flexible metal lithium cathode 3, a flexible polymer solid electrolyte 4 and a flexible carbon-sulfur composite anode 5. The battery adopts a soft package packaging process based on an aluminum plastic film. The specific implementation measures of each part of the novel flexible all-solid-state photo-thermal lithium-sulfur battery are as follows:
1) The specific implementation measures of the flexible optical window are as follows: and (3) punching a single side of the aluminum-plastic film (the aperture is 1.5 cm), adding a layer of hot melt adhesive between the high-light-transmission flexible PI film and the punched aluminum-plastic film by using a high-temperature hot melting process, and then performing heat sealing at about 300 ℃ until the film is firmly adhered.
2) The specific implementation measures of the flexible photo-thermal current collector are as follows: (1) and (3) cleaning flexible ultrathin porous copper with the thickness of about 0.3mm by using dilute hydrochloric acid and ethanol, and drying to obtain the substrate. (2) Annealing at 500 ℃ for 3 hours in the air atmosphere, and depositing amorphous silicon in a PECVD system to obtain the copper oxide-silicon core-shell structure nanowire after growing the copper oxide nanowire. (3) Annealing for 4 hours at 600 ℃ in the hydrogen atmosphere, reducing the copper oxide in the copper oxide-silicon core-shell nanowire into copper and partially separating out from the core to form hybridized copper-silicon core-shell structure nanoparticles which are non-uniformly distributed on the copper-silicon core-shell structure nanowire. (4) Depositing a layer of Al with the thickness of about 5nm on the surface of the copper-silicon nano particles/nano wires in the step (3) by an Atomic Layer Deposition (ALD) process 2 O 3 The film acts as a surface passivation layer. The preparation process of the metal oxide-silicon (germanium) core-shell structure can be Chemical Vapor Deposition (CVD), plasma chemical vapor deposition (PECVD), but is not limited thereto. The gas for in-situ reduction may be a reducing gas such as hydrogen gas or carbon monoxide, or may be a powder having reducing properties such as carbon powder, including but not limited thereto.
3) The flexible lithium metal negative electrode is implemented by the following steps: commercial lithium metal sheets were fabricated into lithium foils of about 200um thickness by a thinning process.
4) The specific implementation measures of the flexible polymer solid electrolyte are as follows: (1) polyethylene oxide powder (PEO, average MV 600000 power, sigma-Aldrich) was mixed with lithium salt (LiTFSI, 99.95% trace metal basis, sigma-Aldrich) in accordance with 18:1, adding Al in an amount of 10% by mass based on the total mass of the mixed powder of polyethylene oxide and lithium salt 2 O 3 Nanoparticles (99.99% metals bases, 80% alpha phase,30nm-50nm Al 2 O 3 nanoparticles, macklin). (2) In PEO, liTFSI and Al 2 O 3 After acetonitrile is added into the mixed powder, the mixture is magnetically stirred for 24 hours until a transparent gel is formed. (3) And (3) dripping the PEO-based polymer gel obtained in the step (2) into a polytetrafluoroethylene template, standing for 48 hours, and forming a film to form the PEO-based polymer solid electrolyte film. The polyethylene oxide powder andthe molar ratio of the lithium salt may be 20: 1. 18: 1. 16: 1. 15: 1. 12:1, etc., including but not limited to. The inorganic filler may be Al 2 O 3 Nanoparticles of Al 2 O 3 The added amount of the nanoparticles may be 5% to 10% by mass of the total mass of the mixed powder of polyethylene oxide and lithium salt, including but not limited thereto. The film-forming template may be a polytetrafluoro template, a stainless steel template, a LAGP solid electrolyte, etc., including but not limited thereto.
5) The specific implementation measures of the flexible carbon-sulfur composite anode are as follows: (1) the ketjen black powder (KB,
EC-600 JD) with elemental sulphur (sublimed sulphur) powder according to 3:7, and manually grinding for 2 hours to form carbon-sulfur mixed powder. (2) And (3) annealing the formed carbon-sulfur mixed powder at the low temperature of 150 ℃ for 5 hours in an argon atmosphere, manually grinding for 1 hour again, and then finishing a second higher-temperature annealing process (annealing at the temperature of 200 ℃ for 2 hours) in the argon atmosphere to form the carbon-sulfur composite positive electrode powder. (3) And adding 10% of PVDF gel and a few drops of NMP solution into the carbon-sulfur composite positive electrode powder, and then uniformly stirring. The PVDF gel is formed by mixing 5% of PVDF with 95% of NMP and then magnetically stirring. (4) And (4) uniformly scraping the carbon-sulfur composite anode formed in the step (3) on the surface of an aluminum foil by using a coating process, and drying at 40 ℃ to form a film. The carbon powder may be ketjen black powder (KB,
EC-600 JD), carbon nanotubes, carbon nanoparticles, graphene, including but not limited to. The mass ratio of the carbon powder to elemental sulfur may be 2: 8. 3:7, including but not limited to. The milling process may be an inert gas ball mill or a manual milling process, including but not limited to. The annealing atmosphere may be an inert gas such as argon, nitrogen, etc., including but not limited thereto. The PVDF gel was formed by mixing 5% PVDF with 95% NMP and magnetic stirring. The addition amount of the PVDF can be 5-10% of the total mass of the carbon-sulfur composite powder. The coating process can be knife coating process or spray coating processCoating processes, including but not limited to.
6) The totally enclosed battery package including the optical window is implemented as follows: (1) and encapsulating the flexible photo-thermal current collector, the flexible metal lithium cathode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite anode in an aluminum plastic film soft package containing a flexible optical window in sequence to realize totally enclosed encapsulation. Wherein the photo-thermal current collector faces the high-transmittance flexible optical window layer. (2) Aluminum is used as a positive conductive tab to be packaged at the flexible carbon-sulfur composite positive terminal, and nickel is used as a negative conductive tab to be packaged between the flexible photo-thermal current collector and the flexible metal lithium foil/lithium film.
The light absorption curve of the novel flexible all-solid-state photo-thermal lithium-sulfur battery negative photo-thermal current collector prepared based on the specific implementation steps is shown in fig. 2, the photo-thermal current collector with the copper-silicon nanoparticle/nanowire structure has a light absorption rate higher than 90% in a wide spectral range from 200nm to 2500nm, and the sunlight absorption rate reaches about 92%. The change curve of the internal temperature of the novel flexible all-solid-state photo-thermal lithium-sulfur battery prepared based on the specific implementation steps along with the illumination intensity and time is shown in figure 3 and is 5.0kW m -2 The temperature of the photo-thermal collector in the illumination cell is rapidly raised to about 70 ℃ (sunlight incident angle: 0 ° vertical incidence), about 55 ℃ (sunlight incident angle: 45 °), and about 50 ℃ (sunlight incident angle: 70 °) after the start of illumination under the simulated solar irradiation of (1). As shown in FIG. 4, the discharge capacity of the flexible all-solid-state photothermal lithium sulfur battery reaches about 900mAh/g and about 260mAh/g at room temperature (about 30 ℃) and low temperature (-60 ℃), respectively. Compared with several typical low-temperature batteries reported internationally at present, the novel flexible all-solid-state photo-thermal lithium-sulfur battery designed and prepared by the inventor has the discharge capacity (-260 mAh g) at 60 ℃ below zero -1 Charge-discharge current density: 80mA g -1 ) Is based on an organic electrolyte lithium ion battery (18 mAh g) -1 Charge-discharge current density: 50mA g -1 14 times of Joule,2018,2,902-913) is based on liquefied gas lithium ion battery (80 mAh g) -1 Charge-discharge current density: 27.4mA g -1 3 times of 2017,356,4263) is the quasi-solid lithium ion battery (work) based on polymer electrolyte reported at presentTemperature: 30 ℃ below zero and 64mAh g -1 Charge-discharge current density: about 64mAh g -1 Multiplying power: 0.1C, advanced Energy materials,2022, 12).
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The above examples are to be construed as merely illustrative and not limitative of the remainder of the disclosure. After reading the description of the present invention, the skilled person can make various changes or modifications to the invention, and these equivalent changes and modifications also fall into the scope of the invention defined by the claims.
Claims (10)
1. A flexible all-solid-state photothermal lithium sulfur battery capable of operating at low temperatures, comprising:
the flexible optical window, the flexible photo-thermal current collector, the flexible metal lithium cathode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite anode are sequentially arranged from top to bottom, the flexible optical window realizes flexible and totally-enclosed battery packaging and light transmission higher than 90%, the flexible photo-thermal current collector combines the metal plasma photo-thermal effect and the light trapping effect of a semiconductor three-dimensional nanostructure to realize efficient light absorption and omnibearing photo-thermal conversion in a full spectrum range, heat is provided for the flexible all-solid-state lithium-sulfur battery based on the polymer all-solid-state electrolyte in room temperature, low temperature and ultralow temperature environments, the flexible metal lithium cathode is the cathode of the flexible all-solid-state lithium-sulfur battery based on the polymer all-solid-state electrolyte and is used for providing lithium ions, the flexible polymer solid-state electrolyte is used for transmission of the lithium ions between the anode and the cathode of the battery, interface between the electrolyte and the anode and the cathode are enhanced to improve the working performance of the battery, the flexible carbon-sulfur composite anode and the carbon composite improve the wettability of an active substance sulfur, and relieve the volume expansion of the sulfur anode in the charging and discharging process.
2. The flexible all-solid-state photothermal lithium sulfur battery capable of working at low temperature according to claim 1, wherein the flexible optical window, the flexible photothermal current collector, the flexible metallic lithium negative electrode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite positive electrode adopt a soft package packaging process based on an aluminum plastic film.
3. The flexible all-solid-state photo-thermal lithium-sulfur battery capable of working at low temperature according to claim 1, wherein the flexible optical window is a high-light-transmission flexible film such as PET/PI/PC (polyethylene terephthalate/polyimide/polycarbonate), and the flexible photo-thermal current collector is of a metal-semiconductor micro-nano composite structure, a metal nanoparticle structure or a metal nanowire structure; the metal lithium cathode is a thinned lithium foil or a sputtered lithium film; the flexible polymer solid electrolyte is a polymer solid electrolyte compounded by PEO, lithium salt and alumina nano particles or a polymer solid electrolyte compounded by PEO and lithium salt; the flexible carbon-sulfur composite positive electrode is a sulfur positive electrode prepared by compounding ketjen black and elemental sulfur, or a sulfur positive electrode prepared by compounding a carbon nano tube and elemental sulfur, or a sulfur positive electrode prepared by compounding graphene and elemental sulfur.
4. A method for preparing a flexible all-solid-state photothermal lithium sulfur battery according to any one of claims 1 to 3, comprising the steps of:
preparing a flexible optical window and packaging a battery system;
preparing a flexible photo-thermal current collector;
preparing a flexible metal lithium cathode;
preparing a flexible polymer solid electrolyte;
and (3) preparing a flexible carbon-sulfur composite positive electrode.
5. The method for preparing the flexible all-solid-state photothermal lithium sulfur battery according to claim 4, wherein the steps of preparing the flexible optical window and packaging the battery system specifically comprise: (1) punching a single side of the aluminum-plastic film (aperture is not limited, determined according to the actual anode and cathode of the battery and a current collector), adding a layer of hot melt adhesive between a high-light-transmission flexible film (PET/PI/PC, light transmittance is more than 90%) and the punched aluminum-plastic film by using a high-temperature hot melting process, and then performing heat sealing at about 300 ℃ until the aluminum-plastic film is firmly pasted; (2) sequentially encapsulating the flexible photo-thermal current collector, the flexible metal lithium cathode, the flexible polymer solid electrolyte and the flexible carbon-sulfur composite anode in an aluminum plastic film soft package containing a flexible optical window to realize totally-enclosed encapsulation; wherein the photo-thermal current collector faces the high-transmittance flexible optical window layer; (3) aluminum is used as a positive conductive tab to be packaged at the flexible carbon-sulfur composite positive terminal, and nickel is used as a negative conductive tab to be packaged between the flexible photo-thermal current collector and the flexible metal lithium foil/lithium film.
6. The method for preparing the flexible all-solid-state photo-thermal lithium-sulfur battery according to claim 4, wherein the steps of preparing the flexible photo-thermal current collector specifically comprise; the preparation method comprises the steps of taking a flexible ultrathin porous metal film with the thickness of 100-0.3 mm as a substrate, growing a metal oxide nanowire on the flexible ultrathin porous metal film by adopting a thermal oxidation process, coating amorphous silicon a-Si or amorphous germanium a-Ge on the flexible ultrathin porous metal film by adopting a semiconductor film preparation process to form a metal oxide/Si (Ge) core-shell structure, and preparing a self-supporting flexible metal-semiconductor micro-nano structure photo-thermal current collector by utilizing high-temperature reduction of the metal oxide and diffusion of metal in a silicon (germanium) shell layer.
7. The method for preparing a flexible all-solid-state photothermal lithium sulfur cell according to claim 5, wherein the metal oxide-silicon (germanium) core-shell structure preparation process comprises Chemical Vapor Deposition (CVD) or plasma chemical vapor deposition (PECVD); the high-temperature reduction of the metal oxide may be performed by a reducing gas such as hydrogen or carbon monoxide, or may be performed by a powder having a reducing property such as carbon powder.
8. The method for preparing the flexible all-solid-state photothermal lithium sulfur battery according to claim 4, wherein the flexible lithium metal negative electrode is prepared by the steps of: commercial lithium metal sheets are made into lithium foils with the thickness less than 100um through a thinning process, or lithium metal films with the thickness less than 50um are prepared through a sputtering coating process.
9. The method for preparing the flexible all-solid-state photothermal lithium sulfur battery according to claim 4, wherein the steps for preparing the flexible polymer solid electrolyte specifically comprise: mixing polyethylene oxide powder PEO and lithium salt LiTFSI according to a certain molar ratio, adding a certain amount of inorganic filler to form mixed powder, adding a certain amount of acetonitrile into the mixed powder, and magnetically stirring for 24 hours to form transparent PEO-based polymer gel. And dripping the obtained PEO-based polymer gel into a mould, standing for 48 hours, and forming a film to form the PEO-based polymer solid electrolyte film.
10. The method for preparing the flexible all-solid-state photo-thermal lithium-sulfur battery according to claim 4, wherein the step of preparing the flexible carbon-sulfur composite positive electrode specifically comprises the following steps: mixing a certain amount of carbon powder with elemental sulfur (sublimed sulfur) powder, and grinding for 2 hours to form carbon-sulfur mixed powder; annealing the formed carbon-sulfur mixed powder at 140-160 ℃ in an argon atmosphere (3-5 hours) to form carbon-sulfur composite positive electrode powder; then, grinding the carbon-sulfur composite positive electrode powder for 1 hour again, and then annealing at 180-220 ℃ (1-2 hours) to form a final carbon-sulfur composite positive electrode (powder); adding a certain amount of PVDF gel and NMP solution into the carbon-sulfur composite positive electrode (powder), uniformly stirring to form a carbon-sulfur positive electrode coating, uniformly coating the carbon-sulfur positive electrode coating on the surface of an aluminum foil or carbon cloth by using a coating process, and drying at 40 ℃ to form a film.
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