CN109713402B - Solar photo-thermal lithium battery capable of working in extreme temperature range and preparation method thereof - Google Patents
Solar photo-thermal lithium battery capable of working in extreme temperature range and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a temperature control device capable of being in a limit temperature rangeThe solar photo-thermal lithium battery 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 it into heat to raise the temperature of the inside of the entire battery assembly, so that it 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 can work in a very low temperature environment. The temperature of the extremely low temperature environment is more than or equal to-200 DEG CoC。
Description
Technical Field
The invention relates to a solar photo-thermal lithium battery capable of working in a limit temperature range and a preparation method thereof, belonging to the technical field of solar photo-thermal batteries.
Background
The development of lithium ion batteries which can work well in cold low-temperature environments (-40 ℃) and hot high-temperature environments (-60 ℃) has important significance for energy storage. At the same time, military and medical grade equipment also further requires that worn batteries be capable of operating in extreme temperature environments. Batteries such as those provided in space shuttles and the like are required to be below-60 ℃. Batteries equipped with medical sterilization devices need to withstand high temperatures of 120 ℃. Compared with the traditional organic liquid battery, the solid-state/all-solid-state lithium ion battery not only has great advantages in the aspects of high energy density, safety and environmental friendliness, but also has good high-temperature operation performance.
However, the low room temperature ionic conductivity of the electrolyte and poor interfacial charge transport in solid state/all-solid state batteries make it difficult to operate the batteries below room temperature. While the temperature plays a decisive role for the electrolyte and the ion transport at the interface. A solid state/all-solid-state battery will lose all of its capacity/power when the temperature drops below zero degrees celsius.
Therefore, most of the presently reported solid state/all-solid state batteries operate at a relatively high temperature (55 ℃ C. to 70 ℃ C.). It is currently a great challenge to develop lithium ion batteries that can operate in a very low temperature environment of less than-200 c to a high temperature environment above 200 c.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a solar photo-thermal battery technology to solve the great challenge that a lithium ion battery is difficult to operate at a low temperature. The technology is applied to the all-solid-state lithium ion battery, so that the effective energy storage of the battery in a wide temperature range from a very low temperature environment to a high temperature environment can be realized.
In order to solve the technical problems, the invention provides a solar photo-thermal lithium battery capable of working in a limit temperature range, which is characterized in that: the solar photo-thermal lithium battery is a closed lithium ion battery or a semi-open lithium ion battery.
The closed lithium ion battery comprises: the positive current collector, the photothermal positive electrode, the electrolyte, the negative electrode and the negative current collector are sequentially arranged from top to bottom; or sequentially comprises a positive current collector, a positive electrode, an electrolyte, a negative electrode and a photo-thermal negative current collector from top to bottom; or sequentially comprises an anode current collector, a photo-thermal anode, an electrolyte, a cathode and a photo-thermal cathode current collector.
The semi-open type lithium ion battery comprises: the solar cell comprises a porous current collector, a photo-thermal anode, an electrolyte, a cathode and a cathode current collector from top to bottom in sequence; or sequentially comprises a porous current collector, a positive electrode, an electrolyte, a negative electrode and a photo-thermal negative current collector from top to bottom; or sequentially comprises a porous current collector, a photo-thermal anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom.
When light is irradiated from the positive electrode side, the photo-thermal positive electrode can capture sunlight and convert it into heat to raise the temperature of the inside of the entire battery module, so that it can operate in a very 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 can work in an extremely low temperature environment.
When light is radiated from the positive electrode and the negative electrode at the same time, the photo-thermal positive electrode and the photo-thermal negative electrode current collectors can capture sunlight at the same time and convert the sunlight into heat to heat the whole battery assembly, so that the battery assembly can work effectively in a very low temperature environment.
The invention further defines the technical scheme as follows: the extremely low temperature environment temperature is more than or equal to-200 ℃, the closed lithium ion battery is an all-solid-state lithium battery, and the working temperature range of the closed lithium ion battery is-200 ℃; the semi-open type lithium ion battery is a lithium-gas battery and can work in an environment with the working extremely low temperature of 200 ℃ below zero. The solar photothermal cell can effectively capture sunlight and convert the sunlight into heat to heat the battery assembly, so that the lithium battery, particularly the all-solid-state battery, can effectively work in the whole temperature range from an ultralow temperature to a high temperature region.
Further, when the closed lithium ion battery sequentially has a positive current collector, a photo-thermal positive electrode, an electrolyte, a negative electrode and a negative current collector structure from top to bottom, an optical window is arranged on the positive current collector; when the closed lithium ion battery sequentially comprises an anode current collector, an anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom, an optical window is arranged below the photo-thermal cathode current collector; an optical window is arranged below the photo-thermal cathode current collector of the semi-open type lithium ion battery.
Further, the positive electrode is a lithium ion battery positive electrode compounded by 5-90% of lithium cobaltate, lithium manganate, lithium iron phosphate or ternary materials, 5-95% of lithium salt, 3-50% of conductive agent and 3-15% of binder by mass percentage; or the lithium-sulfur battery anode is compounded by 5 to 85 mass percent of sulfur active matter, 3 to 50 mass percent of conductive agent and 3 to 15 mass percent of binder; or the anode of the lithium-gas battery is compounded by 3 to 95 mass percent of electronic conductive agent, 3 to 95 mass percent of ion conductive electrolyte powder and 3 to 100 mass percent of catalyst.
Further, the electrolyte is one or a combination of two or more of an organic liquid electrolyte, a solid electrolyte, a molten salt electrolyte, an ionic liquid electrolyte and a lithium salt.
Further, the solid state electrolyte includes, but is not limited to, a perovskite/anti-perovskite ABO3 electrolyte, wherein a ═ Ca, Sr, La; b ═ Al and Ti, the ionic conductivity of which is 10-7 to 10-3, Li1.5Al0.5Ge1.5P3O12/Li1.3Al0.3Ti1.7P3O12 of NASICON type, LAGP/LATP,10-4 to 10-3S cm-1, Li7La3Zr2O12 of garnet type, LLZO,10-4 to 10-3S cm-1 and chalcogenide electrolyte 10-4 to 10-2S cm-1.
Further, the photo-thermal anode is metal or metal oxide RuO with plasma effect2Assembling the composite material of carbon and positive active material by physical vapor deposition or chemical deposition to form a plasma-enhanced photo-thermal positive electrode; or directly compounding a carbon material with high-efficiency light absorption and light conversion effect, an active material and a bonding agent to form the photo-thermal anode; or a photo-thermal anode with metal nano-particles or carbon materials directly deposited on a solid electrolyte sheet.
Further, the photo-thermal negative current collector includes, but is not limited to, a nano material formed by compounding one or two or more of carbon black, acetylene black, SP, Graphene, carbon nanotube CNT, ketjen black or carbon nano fiber, a metal material of aluminum, ruthenium, gold, silver, copper, nickel or cobalt, a corresponding metal oxide, and a semiconductor material of silicon, germanium, tin or titanium dioxide.
Furthermore, the photo-thermal negative current collector is formed by compounding an independent photo-thermal material and a negative current collector; the photothermal material comprises a photothermal conversion film, and the photothermal conversion film is a composite material of one or two or more of the nanostructure of the metal material and the carbon material.
Further, the negative electrode is one or a composite of two or more of an insertion type negative electrode, an alloy type negative electrode and a conversion negative electrode.
The invention also discloses a preparation method of the solar photo-thermal lithium battery capable of working in the limit temperature range, in particular to a solar photo-thermal all-solid-state lithium-air battery based on the LAGP solid electrolyte, which comprises the following steps:
first, theGeO2、Li2CO3、Al2O3And NH4H2PO4According to a mass ratio of 0.7: 0.3: 1.8: 4, mixing, repeatedly performing ball milling and annealing for three times, pressing the obtained powder into a LAGP solid electrolyte wafer, annealing the LAGP solid electrolyte wafer at 900 ℃ for 1 hour, and polishing for later use;
second step, RuO2Mixing the LAGP powder and the CNT according to the mass ratio of 10:100:1, adding 5% of a binder, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, and spin-coating the solution on the LAGP solid electrolyte sheet to obtain a solid electrolyte sheet with the photo-thermal anode;
thirdly, annealing for 15min at 500 ℃ in Ar atmosphere;
and fourthly, packaging the aluminum mesh positive current collector, the LAGP solid electrolyte sheet coated with the photo-thermal positive electrode, the metal lithium negative electrode and the copper foil negative current collector into a soft package battery from top to bottom by adopting an aluminum plastic film.
The invention has the beneficial effects that: the invention firstly provides a solar photo-thermal battery technology, in particular to a solar photo-thermal solid state/full solid state lithium ion battery technology. The solid state/all solid state battery design using solid electrolyte ensures the excellent cycling performance of the battery system at high temperatures. The photo-thermal technology is introduced into the lithium ion battery, the key challenge of low lithium mobility at low temperature of an electrode material electrolyte/solid electrolyte and an interface thereof is solved by utilizing the solar photo-thermal lithium battery technology for the first time, and the solid/all-solid lithium ion battery capable of working at extremely low temperature is developed. The invention improves the ion migration of the electrolyte and the interface of the lithium ion battery at low temperature by capturing sunlight and converting the sunlight into heat, thereby enabling the lithium ion battery to work at ultralow temperature. Operation in a wide temperature range from extremely low temperature to high temperature can also be achieved for solid state/all-solid state batteries. In the structure of the photo-thermal battery, for the structure of irradiating light from the positive electrode, the photo-thermal positive electrode is directly contacted with the electrolyte, and the converted heat can be quickly and efficiently transferred to the electrolyte, the negative electrode and even the whole battery assembly, so that the battery can keep a relatively high working temperature at ultralow temperature. For the battery structure polished from the negative electrode side, besides the electrolyte and the electrode material are kept at a high working temperature, if the negative electrode uses the metal lithium, the heat generated by the photo-thermal negative electrode current collector can be directly transferred to the negative electrode, and the temperature of the metal lithium negative electrode is increased to a certain extent to reach the aim of melting the metal lithium dendrite and inhibiting the growth of the metal lithium dendrite of the negative electrode. The solar photo-thermal lithium battery can work even in an extremely low temperature environment of-200 ℃ to a high temperature environment above 200 ℃, so that the lithium ion battery can be well circulated in a wide limit temperature range; the technology is a great progress in the development direction of the lithium battery in the future, and is worth popularizing and using in the limit environments of aerospace, medical treatment and the like.
Drawings
Fig. 1 is a schematic diagram of four cell structures according to example 1 of the present invention.
In which, fig. a and b show the structure of the cell with light from the positive electrode side, and fig. c and d show the structure of the cell with light from the negative electrode side.
Fig. 2 is a schematic diagram of a working performance test of a solar photo-thermal all-solid-state lithium-air battery with a lag solid electrolyte according to an embodiment of the present invention at an extreme temperature.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
The solar photo-thermal lithium battery capable of working in the limit temperature range provided by the invention has the working principle based on the photo-induced thermal effect at the limit temperature. The solar cell can capture solar light through the positive electrode side and can also capture the solar light through the negative electrode side.
Can be a closed all-solid-state lithium ion battery or a semi-open lithium-gas ion battery.
The closed lithium ion battery has three structural forms:
s1, sequentially comprising an anode current collector, a photo-thermal anode, an electrolyte, a cathode and a cathode current collector from top to bottom.
And S2, sequentially comprising an anode current collector, an anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom.
S3, sequentially comprising an anode current collector, a photo-thermal anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom;
the semi-open type lithium ion battery also has three structural forms:
D1. the solar cell comprises a porous current collector, a photo-thermal anode, an electrolyte, a cathode and a cathode current collector from top to bottom in sequence.
D2. The solar cell comprises a porous current collector, a positive electrode, an electrolyte, a negative electrode and a photo-thermal negative current collector from top to bottom in sequence.
D3. The solar cell comprises a porous current collector, a photo-thermal anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom in sequence.
When light is irradiated from the positive electrode side, the cell photothermal positive electrode of the S1, S3, D1, D3 structure can absorb sunlight and convert it into heat to increase the temperature of the electrolyte or the entire cell assembly; when light is radiated from the negative electrode side, the cell photo-thermal negative electrode current collectors with the structures of S2, S3, D2 and D3 can absorb sunlight and convert the sunlight into heat which is transferred to an electrolyte and a positive electrode through the negative electrode, so that the whole cell assembly is heated; when light is radiated from the two sides of the positive electrode and the negative electrode, the photo-thermal positive electrode and the photo-thermal negative electrode current collectors can capture sunlight simultaneously and convert the sunlight into heat to heat the whole battery assembly, so that the battery assembly can work effectively in a very low temperature environment.
The illumination light source of the invention can be sunlight, also can be AM1.5 and xenon lamp, and the illumination power is from 103W m-2To 106W m2。
The closed lithium ion battery and the semi-open lithium ion battery can work at a limit temperature, and particularly, the working temperature range of the solar photo-thermal solid state/full solid state lithium ion battery can reach-200 ℃ to 200 ℃.
When the closed lithium ion battery is of a positive current collector, a photo-thermal positive electrode, an electrolyte, a negative electrode and a negative current collector structure from top to bottom in sequence, an optical window is arranged on the positive current collector.
When the closed lithium ion battery is from last to being anodal mass flow body, anodal, electrolyte, negative pole and light and heat negative pole mass flow body down in proper order, then be equipped with the optics window below the light and heat negative pole mass flow body.
An optical window is arranged below the photo-thermal cathode current collector of the semi-open type lithium ion battery. The optical window in this embodiment is made of a material having a high light transmittance, such as quartz or transparent glass, with a thickness of 0.2mm to 1 cm.
Preferably, the lithium ion battery is composed of lithium cobaltate, lithium manganate, lithium iron phosphate, and LiNi which is a ternary material0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2,LiNi0.5Co0.2Mn0.2O2,LiNiCoMnO2,LiNiCoAlO25 to 90 percent of lithium salt LiBF4、LiPF65-95%, one or more of conductive agent carbon black, acetylene black, SP, graphene, carbon nano tube, Ketjen black, carbon nano fiber and the like, and 3-50% of binder PVDF, PVA and the like, and 3-15%. The positive electrode for lithium-sulfur batteries may be a positive electrode obtained by compounding 5 to 85% of a sulfur active material, 3 to 50% of one or a combination of two or more of conductive agent carbon black, acetylene black, SP, graphene, carbon nanotubes, Ketjen black, carbon nanofibers and the like, and 3 to 15% of a binder PVA, PVDF and the like. Or lithium-air, lithium-oxygen, lithium-carbon dioxide and lithium-nitrogen batteries of lithium-gas batteries, and one or more of electronic conductive agent carbon black, acetylene black, SP, graphene, carbon nano tube, Ketjen black, carbon nano fiber and the like which account for 3-9 percent in the lithium-gas batteries, and ion-conductive electrolyte powder Li1.5Al0.5Ge1.5P3O12/Li1.3Al0.3Ti1.7P3O12、Li7La3Zr2O12、Perovskite/Antiperovskite ABO3A ═ Ca, Sr, La; 3-95% of B ═ Al, Ti and the like, and Ru and RuO catalysts2,Au,Fe、Ni、Co、RuO2Transition metal compounds such as NiO and the like and non-noble metal catalysis3-100% of a non-metal catalyst such as N-doped carbon material, and the like.
Preferably, the electrolyte of the present invention is one or a combination of two or more of an organic liquid electrolyte, a solid electrolyte, a molten salt electrolyte, an ionic liquid electrolyte, and a lithium salt.
Preferably, the solid electrolyte includes, but is not limited to, a perovskite/anti-perovskite ABO3 electrolyte, wherein a ═ Ca, Sr, La; b ═ Al and Ti, the ionic conductivity of which is 10-7 to 10-3, Li1.5Al0.5Ge1.5P3O12/Li1.3Al0.3Ti1.7P3O12 of NASICON type, LAGP/LATP,10-4 to 10-3S cm-1, Li7La3Zr2O12 of garnet type, LLZO,10-4 to 10-3S cm-1 and chalcogenide electrolyte 10-4 to 10-2S cm-1.
Preferably, the photothermal positive electrode may be a plasma-enhanced photothermal positive electrode formed by assembling metal Al, Ru, Au, Ag, Cu, Ni, Co, etc./metal oxide RuO2 having a plasma effect on a composite material of carbon and a positive electrode active material by a physical vapor deposition or chemical deposition method. Or directly compounding one or more of carbon black, acetylene black, SP, graphene, carbon nanotubes, Ketjen black, carbon nanofibers and the like with high-efficiency light absorption and light conversion effects with an active material and a binder to form the photo-thermal anode. For lithium-gas batteries, it is also possible to have a photo-thermal anode with metal nanoparticles or carbon material deposited directly on the solid electrolyte sheet.
Preferably, the photo-thermal negative current collector includes, but is not limited to, carbon materials such as carbon black, acetylene black, SP, Graphene, carbon nanotube CNT, ketjen black, carbon nanofiber, etc., metal materials such as aluminum Al, ruthenium Ru, gold Au, silver Ag, copper Cu, nickel Ni, cobalt Co, etc., and corresponding metal oxides, silicon Si, germanium Ge, tin Sn, titanium dioxide TiO, etc2And one or two or more of semiconductor materials. When the film is illuminated, the photo-thermal negative collector film can convert light into heat to heat the negative electrode, the solid electrolyte and the positive electrode.
Preferably, the photo-thermal negative current collector can be formed by compounding an independent photo-thermal material and a negative current collector; the photothermal material comprises a photothermal conversion film, and the photothermal conversion film is a composite material of one or two or more of the nanostructure of the metal material and the carbon material.
The negative electrode may preferably be an insertion-type negative electrode carbon, graphene, TiO2, LiTiO2, or the like, an alloy-type negative electrode Si, Ge, Sn, Al, or the like, or a conversion negative electrode (one or a combination of two or more of Fe2O3, CuO, CoO2, or the like.
The solar photo-thermal lithium electronic battery of the invention comprises, but is not limited to, conventional lithium ion batteries based on organic liquid, lithium-gas batteries, solid/all solid lithium ion batteries, solid/all solid lithium-sulfur batteries, solid/all solid lithium-air batteries, solid/all solid lithium-carbon dioxide batteries, solid/all solid lithium-nitrogen batteries, and related batteries such as fused salt batteries and lithium-gas batteries, and the like, and hybrid batteries.
At low temperatures, the cell is designed to efficiently capture sunlight and convert it to heat for transfer to all cell components including electrolyte/solid electrolyte, electrode materials and current collectors by designing the photo-thermal positive electrode fig. 1a,1b or photo-thermal negative electrode current collector fig. 1c,1 d. So that the whole battery can maintain a higher working temperature and good cycle performance even under the external environment with extremely low temperature. At room temperature, the heat generated by light can keep the battery in a higher-temperature working environment, so that the storage and transmission of charges in the battery are improved, and the capacity/energy density and the cycle performance of the battery can be effectively improved.
The embodiment discloses a solar photo-thermal all-solid-state lithium-air battery based on a LAGP solid electrolyte, and the preparation method comprises the following steps:
first, GeO2、Li2CO3、Al2O3And NH4H2PO4The powder of (2) is mixed according to the mass percentage of 0.7: 0.3: 1.8: 4, mixing, repeatedly performing ball milling and annealing for three times, pressing the obtained powder into a LAGP solid electrolyte wafer with the diameter of 1.6cm, annealing the LAGP solid electrolyte wafer at 900 ℃ for 1 hour, and polishing for later use;
second step, RuO2Mixing the LAGP powder and the CNT according to the mass ratio of 10:100:1, adding 5% of a binder, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, and spin-coating the solution on the LAGP solid electrolyte sheet to obtain a solid electrolyte sheet with the photo-thermal anode;
thirdly, annealing for 15min at 500 ℃ in Ar atmosphere;
and fourthly, packaging the aluminum mesh positive current collector, the LAGP solid electrolyte sheet coated with the photo-thermal positive electrode, the metal lithium negative electrode and the copper foil negative current collector into a soft package battery from top to bottom by adopting an aluminum plastic film.
The working performance test of the solar photo-thermal all-solid-state lithium-air battery with the LAGP solid electrolyte at the limiting temperature is as follows:
FIG. 2a is a graph of the cycling performance of a photo-thermal all-solid-state lithium-air battery in a dry ice-78 deg.C to-73 deg.C environment; fig. 2b shows the temperature of each component of the all-solid-state photothermal cell stabilized at-78 deg.c to-73 deg.c in dry ice as a function of the illumination time.
As can be seen from fig. 2a, the all-solid-state battery exhibits excellent cycle performance at a temperature of-78 c, and the photo-thermal positive electrode thereof exhibits an effective photo-heating effect by heating the inside of the battery from an ultra-low temperature of-78 c to 70 c by capturing sunlight and converting into heat. Therefore, the internal temperature of the cell is further reduced to 20 ℃ and below reported in the literature, and the external working environment temperature of the photo-thermal all-solid-state cell adopted by the cell can be further reduced from-78 ℃. Plus the currently mature adiabatic and concentrating technology, it is fully feasible to achieve operation of all-solid-state batteries at-200 ℃. For example, Ye et al, Adv. EnergyMater.2017,7,1601657, at Tianjin university report that Ru nanoparticles are used as photo-thermal catalysts to reduce CO2In the Xe lamp, the surface temperature of Ru nanoparticles on different carriers is as high as 280 ℃ to 350 ℃. Chen et al, nature energy, 2016,16126, in ma ken, proposed the concept of thermal aggregation and achieved a 100 c water vapor temperature in the sun through polymer foam.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (8)
1. The solar photo-thermal lithium battery capable of working in a limit temperature range is characterized in that: the solar photo-thermal lithium battery is a closed lithium ion battery or a semi-open lithium ion battery;
the closed lithium ion battery comprises: the solar cell comprises a positive current collector, a photo-thermal positive electrode, an electrolyte, a negative electrode and a negative current collector from top to bottom in sequence, wherein an optical window is arranged on the positive current collector; or the solar cell sequentially comprises an anode current collector, an anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom, and an optical window is arranged below the photo-thermal cathode current collector; or the solar cell sequentially comprises an anode current collector, a photo-thermal anode, an electrolyte, a cathode and a photo-thermal cathode current collector, and optical windows are arranged on the anode current collector and the photo-thermal cathode current collector;
the semi-open type lithium ion battery comprises: the solar cell comprises a porous current collector, a photo-thermal anode, an electrolyte, a cathode and a cathode current collector from top to bottom in sequence; or sequentially comprises a porous current collector, a positive electrode, an electrolyte, a negative electrode and a photo-thermal negative current collector from top to bottom; or sequentially comprises a porous current collector, a photo-thermal anode, an electrolyte, a cathode and a photo-thermal cathode current collector from top to bottom; an optical window is arranged below the photo-thermal negative current collector;
when light is irradiated from the positive electrode side, the photothermal positive electrode can capture sunlight and convert it into heat to raise the temperature of the inside of the entire battery assembly, so that it 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 works in a very low temperature environment;
when light is radiated from the positive electrode and the negative electrode at the same time, the photo-thermal positive electrode and the photo-thermal negative electrode current collectors can capture sunlight at the same time and convert the sunlight into heat to heat the whole battery assembly, so that the battery assembly can effectively work in an extremely low temperature environment;
the temperature of the extremely low temperature environment is more than or equal to-200 DEG CoC, the closed typeThe lithium ion battery is an all-solid-state lithium battery, and the working temperature range of the lithium ion battery is-200 DEG CoC-200 ℃; the semi-open type lithium ion battery is a lithium-gas battery and can work at the extremely low temperature of 200 ℃ below zerooAnd C, working in an environment.
2. The solar photothermal lithium cell operable in a limiting temperature range according to claim 1, wherein: the positive electrode is a lithium ion battery positive electrode compounded by 5-90% of lithium cobaltate, lithium manganate, lithium iron phosphate or ternary materials, 5-95% of lithium salt, 3-50% of conductive agent and 3-15% of binder by mass percentage;
or 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 in percentage by mass;
or the lithium-gas battery positive electrode is formed by compounding 3-95% of the electronic conductive agent, 3-95% of the ion conductive electrolyte powder and 3-100% of the catalyst in percentage by mass.
3. The solar photo-thermal lithium battery capable of working in a limit temperature range according to claim 2, characterized in that: the electrolyte is one or the combination of two or more of organic liquid electrolyte, solid electrolyte, molten salt electrolyte, ionic liquid electrolyte and lithium salt.
4. The solar photo-thermal lithium battery capable of working in a limit temperature range according to claim 3, characterized in that: the solid electrolyte includes, but is not limited to, perovskite/anti-perovskite ABO3Electrolyte, wherein A = Ca, Sr, La, B = Al, Ti, and the ionic conductivity is 10-7~10-3S cm-1Li of the NASICON type1.5Al0.5Ge1.5P3O12/Li1.3Al0.3Ti1.7P3O12，LAGP/LATP, 10-4~10-3S cm-1Garnet type Li7La3Zr2O12，LLZO, 10-4~10-3S cm-1And a sulfur-based electrolyte 10-4~10-2S cm-1。
5. The solar photo-thermal lithium battery capable of working in a limit temperature range according to claim 4, wherein: the photo-thermal anode is metal or metal oxide RuO with plasma effect2Assembling the composite material of carbon and positive active material by physical vapor deposition or chemical deposition to form a plasma-enhanced photo-thermal positive electrode;
or directly compounding a carbon material with high-efficiency light absorption and light conversion effect, an active material and a bonding agent to form the photo-thermal anode;
or a photo-thermal anode with metal nano-particles or carbon materials directly deposited on a solid electrolyte sheet.
6. The solar photo-thermal lithium battery capable of working in a limit temperature range according to claim 5, wherein: the photo-thermal negative current collector comprises but is not limited to a nano material formed by compounding one or two or more of carbon black, acetylene black, SP, Graphene, carbon nano tube CNT, Ketjen black or carbon nano fiber carbon material, aluminum, ruthenium, gold, silver, copper, nickel or cobalt metal material and corresponding metal oxide, and silicon, germanium, tin or titanium dioxide semiconductor material.
7. The solar photo-thermal lithium battery capable of working in a limit temperature range according to claim 6, wherein: the photo-thermal negative current collector is formed by compounding an independent photo-thermal material and a negative current collector; the photothermal material comprises a photothermal conversion film, and the photothermal conversion film is a composite material of one or two or more of the nanostructure of the metal material and the carbon material.
8. The solar photo-thermal lithium battery capable of working in a limit temperature range according to claim 7, characterized in that: the solar photo-thermal lithium battery is a solar photo-thermal all-solid-state lithium-air battery based on LAGP solid electrolyte, and the preparation method comprises the following steps:
first, GeO2、 Li2CO3、 Al2O3And NH4H2PO4According to a mass ratio of 0.7: 0.3: 1.8: 4, mixing, repeatedly performing ball milling and annealing for three times, pressing the obtained powder into a LAGP solid electrolyte wafer, annealing the LAGP solid electrolyte wafer for 1 hour at 900 ℃, and polishing for later use;
second step, RuO2Mixing the LAGP powder and the CNT according to the mass ratio of 10:100:1, adding 5% of a binder, adding a proper amount of N-methyl pyrrolidone, uniformly stirring, and spin-coating the solution on the LAGP solid electrolyte sheet to obtain a solid electrolyte sheet with the photo-thermal anode;
third, 500 in Ar atmosphereoC, annealing for 15 min;
and fourthly, packaging the aluminum mesh positive current collector, the LAGP solid electrolyte sheet coated with the photo-thermal positive electrode, the metal lithium negative electrode and the copper foil negative current collector into a soft package battery from top to bottom by adopting an aluminum plastic film.
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