CN109713402A - It can be in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works - Google Patents
It can be in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works Download PDFInfo
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- CN109713402A CN109713402A CN201811628910.9A CN201811628910A CN109713402A CN 109713402 A CN109713402 A CN 109713402A CN 201811628910 A CN201811628910 A CN 201811628910A CN 109713402 A CN109713402 A CN 109713402A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to a kind of solar energy optical-thermal lithium batteries that can be worked in temperature range limit, including closed lithium ion battery and semi open model lithium-gas cell.When illumination is irradiated from positive side, photo-thermal anode can capture sunlight and convert thereof into heat to improve the temperature of the inside of entire battery component, so as to work in the low temperature environment of pole；When illumination is irradiated from cathode side, photo-thermal negative current collector, which absorbs sunlight and converts thereof into heat, passes to electrolyte and anode through cathode, to reach the heating of the component to entire battery, it is made to work in the low temperature environment of pole.Extremely low temperature environment temperature >=-200oC。
Description
Technical field
It can belong in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works the present invention relates to a kind of
Solar energy optical-thermal battery technology field.
Background technique
Development can work very well in cold low temperature environment (~-40 DEG C) and the hot environment (~60 DEG C) of sweltering heat
Lithium ion battery have great importance for the storage of the energy.Meanwhile military and medical grade equipment is also further wanted
Ask the battery carried on the back and worn that can operate in extreme-temperature environment.The battery of such as space shuttle outfit need -60 DEG C with
Under.Battery provisioned in medical bactericidal unit needs resistance to 120 DEG C of high temperature.Compared to traditional organic liquid battery, solid-state/complete
Solid lithium ion battery not only illustrates big advantage at high-energy density, safety and environmental-friendly aspect, while
Illustrate good high-temperature operation performance.
But in solid-state/all-solid-state battery the low conductivity at room temperature of electrolyte and difference interface charge transmit so that
Battery is difficult to work below room temperature.And for the Ion transfer of electrolyte and interface, temperature plays conclusive effect.When
When temperature is reduced to zero degrees celsius or less, solid-state/all-solid-state battery will lose its all capacity/power.
Therefore, the solid-state/all-solid-state battery reported at present is mostly all in a relatively high temperature (55 DEG C~70 DEG C)
Lower work.Development can one less than -200 DEG C pole low temperature environment to 200 DEG C or more hot environment operate lithium ion
Battery is a current huge challenge.
Summary of the invention
The technical problem to be solved by the present invention is to the shortcomings that overcoming the prior art, provide a kind of solar energy thermal cell
Technology solves the huge challenge that lithium ion battery is difficult to operate at low temperature.By the technical application to all-solid lithium-ion battery
In battery may be implemented in effective energy storage of the wide temperature range of pole low temperature environment to hot environment.
In order to solve the above technical problems, the present invention provides a kind of solar energy optical-thermal lithium that can be worked in temperature range limit
Battery, it is characterised in that: the solar energy optical-thermal lithium battery is closed lithium ion battery or semi open model lithium ion battery.
The closed lithium ion battery: successively including plus plate current-collecting body, photo-thermal anode, electrolyte, cathode from top to bottom
And negative current collector；It or from top to bottom successively include plus plate current-collecting body, anode, electrolyte, cathode and photo-thermal negative current collector；
It or successively include plus plate current-collecting body, photo-thermal anode, electrolyte, cathode and photo-thermal negative current collector.
The semi open model lithium ion battery: from top to bottom successively include porous current collector, photo-thermal anode, electrolyte, bear
Pole and negative current collector；It or from top to bottom successively include porous current collector, anode, electrolyte, cathode and photo-thermal negative pole currect collecting
Body；It or from top to bottom successively include porous current collector, photo-thermal anode, electrolyte, cathode, photo-thermal negative current collector.
When illumination is irradiated from positive side, photo-thermal anode can capture sunlight and convert thereof into heat to improve entirely
The temperature of the inside of battery component, so as to work in the low temperature environment of pole.
When illumination is irradiated from cathode side, photo-thermal negative current collector absorbs sunlight and converts thereof into heat to be passed through cathode
Electrolyte and anode are passed, to reach the heating of the component to entire battery, makes its work in the low temperature environment of pole.
When light is irradiated from anode and cathode simultaneously, photo-thermal anode and photo-thermal negative pole currect collecting physical efficiency capture sunlight simultaneously simultaneously
Heat is converted thereof into heat entire battery component, it is made effectively to work in the low temperature environment of pole.
The technical solution that the present invention further limits are as follows: extremely low temperature environment temperature >=-200 DEG C, the closed lithium
Ion battery is solid lithium battery, and operating temperature range is -200 DEG C~200 DEG C；The semi open model lithium ion battery is
Lithium-gas cell can work under extremely low -200 DEG C of environment of temperature that work.The solar energy thermal cell can effectively capture too
Sunlight is simultaneously converted into heat to heat battery component to make lithium battery, especially all-solid-state battery can be in ultralow temperature to height
It effectively works in the entire temperature range of warm area.
Further, when the closed lithium ion battery is followed successively by plus plate current-collecting body, photo-thermal anode, electrolysis from top to bottom
When matter, cathode and negative current collector structure, then the upper surface of described plus plate current-collecting body is equipped with optical window；When the closed lithium
It is when ion battery is followed successively by plus plate current-collecting body, anode, electrolyte, cathode and photo-thermal negative current collector from top to bottom, then described
Optical window is equipped with below photo-thermal negative current collector；Below the photo-thermal negative current collector of the semi open model lithium ion battery
Equipped with optical window.
Further, the anode be by mass percent be 5%~90% cobalt acid lithium, LiMn2O4, LiFePO4 or
The lithium-ion electric that ternary material, 5%~95% lithium salts, 3%~50% conductive agent and 3%~15% binder are combined
Pond anode；Or it is answered by the sulphur active matter of mass percent 5%~85%, 3%~50% conductive agent and 3%~15% binder
The anode of lithium-sulfur cell made of conjunction；Or by mass percent 3%~95% electronic conductor, 3%~95% ionic conduction
Electrolyte powder and 3%~100% catalyst be combined lithium-gas cell anode.
Further, the electrolyte is liquid organic electrolyte, solid electrolyte, molten salt electrolyte, ionic liquid
The combination of one or both of electrolyte and lithium salts or more.
Further, the solid electrolyte includes but is not limited to Ca-Ti ore type/anti-perovskite type ABO3 electrolyte,
Middle A=Ca, Sr, La；B=Al, Ti, ionic conductivity in 10-7~10-3, NASICON type
Li1.5Al0.5Ge1.5P3O12/Li1.3Al0.3Ti1.7P3O12, LAGP/LATP, 10-4~10-3S cm-1, carbuncle type
Li7La3Zr2O12, LLZO, 10-4~10-3S cm-1 and sulphur system electrolyte 10-4~10-2S cm-1.
Further, the photo-thermal anode is the metal or metal oxide RuO that will have plasma effect2Pass through object
Physical vapor deposition or the method for chemical deposition, which are assembled on the composite material of carbon and positive electrode active material, forms plasma enhancing
Photo-thermal anode；Or directly the carbon material, active material and adhesive that turn effect with efficient light absorption and light are combined
Photo-thermal anode；Or directly in the photo-thermal of solid electrolyte on piece depositing metallic nanoparticles or carbon material anode.
Further, the photo-thermal negative current collector includes but is not limited to by carbon black, acetylene black, SP, graphene
Graphene, carbon nanotube CNT, Ketjen black or carbon nano-fiber, aluminium, ruthenium, gold, silver, copper, nickel or cobalt metal material and corresponding gold
Belong to oxide, one or both of silicon, germanium, tin or titanium dioxide semiconductor material and the two or more nanometer materials being combined
Material.
Further, the photo-thermal negative current collector is combined by independent optothermal material and negative current collector；Institute
Stating optothermal material includes photothermal conversion film, and the photothermal conversion film is in the nanostructure and the carbon material of the metal material
One or two or more composite material.
Further, the cathode is one of insert type cathode, alloy type cathode and conversion cathode or two kinds
Or more it is compound.
The invention also discloses a kind of preparation methods of solar energy optical-thermal lithium battery that can be worked in temperature range limit, especially
It is a kind of all solid state lithium-air battery of the solar energy optical-thermal based on LAGP solid electrolyte, and preparation method includes following
Step:
The first step, by GeO2、Li2CO3、Al2O3And NH4H2PO4Powder according to mass ratio 0.7:0.3:1.8:4 mix, instead
Multiple ball milling and annealing three times, is pressed into LAGP solid electrolyte disk for gained powder, LAGP solid electrolyte disk is existed
900 ° of sanding and polishings after re-annealing 1 hour are stand-by；
Second step, by RuO2, LAGP powder and CNT be added after mixing according to the ratio of mass percent 10:100:1 and bond
Agent 5%, suitable N-Methyl pyrrolidone being added solution being spin-coated on LAGP solid electrolyte on piece after mixing evenly can obtain
To the solid electrolyte piece for being prepared with photo-thermal anode；
Third step, under an ar atmosphere 500 DEG C of annealing 15min；
4th step, from top to bottom by aluminium net plus plate current-collecting body, be coated with LAGP solid electrolyte piece, the lithium metal of photo-thermal anode
Cathode and copper foil negative current collector use aluminum plastic film to be packaged into soft-package battery.
The beneficial effects of the present invention are: present invention firstly provides solar energy optical-thermal battery technology, especially solar energy
Thermosetting state/all-solid lithium-ion battery technology.The cell body has been ensured using solid-state/all-solid-state battery design of solid electrolyte
It is cycle performance excellent at high temperature.Photothermal technique is introduced in lithium ion battery to be put forward for the first time and utilizes solar energy optical-thermal lithium
Battery technology to solve electrode material electrolyte/solid electrolyte and its interface, choose at low temperature by the low key of lithium transport factor
Solid-state/the all-solid lithium-ion battery that can be worked at extremely low temperatures is developed in war.The present invention be by capture sunlight and by its
Heat is converted into improve lithium ion battery electrolyte and the Ion transfer of interface at low temperature, thus can be in ultralow temperature
Lower work.Operation within the scope of the wide warm area of extremely low temperature to high temperature can also be realized for solid-state/all-solid-state battery.In this hair
In bright photo-thermal cell structure, for surveying the structure of irradiation from anode, photo-thermal anode is directly contacted with electrolyte, can will be converted
Heat pass to electrolyte, cathode or even entire battery component quickly and efficiently to making battery also keep one under ultralow temperature
A relatively high operating temperature.For the battery structure from the polishing of cathode side, in addition to also keeping electrolyte and electrode material
Outside one mutually high operating temperature, if cathode uses lithium metal, the heat that photo-thermal negative current collector generates can be directly passed to
Cathode also while to a certain extent improves the temperature of lithium anode and inhibits negative metal lithium to reach molten metal Li dendrite
The growth of dendrite.Solar energy optical-thermal lithium battery of the invention even can be in -200 DEG C of pole low temperature environment to 200 DEG C or more
Hot environment work, to realize lithium ion battery good circulation in wide temperature range limit；The technology will be future
One huge advance of lithium battery developing direction is worth promoting the use of under the extreme environments such as space flight, medical treatment.
Detailed description of the invention
Fig. 1 is four kinds of battery structure schematic diagrames of the embodiment of the present invention 1.
Wherein figure a is the battery structure from positive side polishing with b is schemed, and figure c and figure d are the battery from the polishing of cathode side
Structure.
Fig. 2 is all solid state lithium-air battery of solar energy optical-thermal of LAGP of embodiment of the present invention solid electrolyte in limit temperature
Working performance test schematic diagram under degree.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and detailed description.
Embodiment 1
The solar energy optical-thermal lithium battery provided by the invention that can be worked in temperature range limit, the battery is under limiting temperature
Fuel factor of the working principle based on photoinduction.The battery can capture solar energy by positive side, can also be by negative
Capture sunlight in pole side.
It can be closed all-solid lithium-ion battery or semi open model lithium-gas ion battery.
There are three types of structure types for closed lithium ion battery:
It S1. from top to bottom successively include plus plate current-collecting body, photo-thermal anode, electrolyte, cathode and negative current collector.
It S2. from top to bottom successively include plus plate current-collecting body, anode, electrolyte, cathode and photo-thermal negative current collector.
It S3. from top to bottom successively include plus plate current-collecting body, photo-thermal anode, electrolyte, cathode and photo-thermal negative current collector；
Also there are three types of structure types for semi open model lithium ion battery:
It D1. from top to bottom successively include porous current collector, photo-thermal anode, electrolyte, cathode and negative current collector.
It D2. from top to bottom successively include porous current collector, anode, electrolyte, cathode and photo-thermal negative current collector.
It D3. from top to bottom successively include porous current collector, photo-thermal anode, electrolyte, cathode and photo-thermal negative current collector.
When illumination is irradiated from positive side, the cell light anlogous pole of S1, S3, D1, D3 structure can absorb sunlight simultaneously
Heat is converted thereof into improve the temperature of electrolyte or entire battery component；When illumination from cathode side irradiate when, S2, S3, D2,
The cell light antilogous pole collector of D3 structure, which can absorb sunlight and convert thereof into heat, passes to electrolyte and just through cathode
Pole, to reach the heating of the component to entire battery；When light is irradiated from anode and cathode two sides simultaneously, photo-thermal anode and light
Antilogous pole afflux physical efficiency captures sunlight simultaneously and converts thereof into heat to heat entire battery component, makes it in pole low temperature environment
In effectively work.
Illumination light source of the invention can be sunlight, be also possible to AM1.5 and xenon lamp, and illumination power is from 103W m-2It arrives
106W m2。
The closed lithium ion battery and semi open model lithium ion battery can work under limiting temperature, especially the sun
Energy photo-thermal solid-state/all-solid lithium-ion battery, operating temperature range can reach -200 DEG C~200 DEG C.
When closed lithium ion battery is followed successively by plus plate current-collecting body, photo-thermal anode, electrolyte, cathode from top to bottom and bears
When the current collector structure of pole, then the upper surface of described plus plate current-collecting body is equipped with optical window.
When the closed lithium ion battery is followed successively by plus plate current-collecting body, anode, electrolyte, cathode and light from top to bottom
When antilogous pole collector, then optical window is equipped with below the photo-thermal negative current collector.
Optical window is equipped with below the photo-thermal negative current collector of semi open model lithium ion battery.Optical window in this implementation
Mouth is using good materials of translucency such as quartz, transparent glass of the thickness between 0.2mm to 1cm.
Preferably, can be by cobalt acid lithium, LiMn2O4, LiFePO4, ternary material for lithium ion battery
LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.3O2,LiNi0.5Co0.2Mn0.2O2,LiNiCoMnO2,LiNiCoAlO2In
One kind, accounting 5%~90%, lithium salts LiBF4、LiPF6Deng, accounting 5%~95%, conductive agent carbon black, acetylene black, SP, graphite
Compound, the accounting 3%~50% and bonding of one or both of alkene, carbon nanotube, Ketjen black, carbon nano-fiber etc. or more
3%~15% anode being combined such as agent PVDF, PVA.Be also possible to lithium-sulfur cell by sulphur active matter, accounting 5%~
85%, one or both of conductive agent carbon black, acetylene black, SP, graphene, carbon nanotube, Ketjen black, carbon nano-fiber etc. and
Above is compound, accounting 3%~50% and binder PVA, PVDF etc., the anode that accounting 3%~15% is combined.It can be with
It is lithium-gas cell lithium-air, lithium-oxygen, lithium-carbon dioxide, lithium-nitrogen battery by electronic conductor carbon black, acetylene
One or both of black, SP, graphene, carbon nanotube, Ketjen black, carbon nano-fiber etc. or more it is compound, accounting 3%~
9%, the electrolyte powder Li of ionic conduction1.5Al0.5Ge1.5P3O12/Li1.3Al0.3Ti1.7P3O12、Li7La3Zr2O12、
Perovskite/Antiperovskite ABO3A=Ca, Sr, La；B=Al, Ti etc., accounting 3%~95% and catalyst Ru,
RuO2,Au,Fe、Ni、Co、RuO2, including the transistion metal compounds such as NiO and non-precious metal catalyst and N- doping carbon material etc.
Non-metallic catalyst etc., the anode that accounting 3%~100% is combined.
Preferably, electrolyte of the invention is liquid organic electrolyte, solid electrolyte, molten salt electrolyte, ion
The combination of one or both of liquid electrolyte and lithium salts or more.
Preferably, solid electrolyte includes but is not limited to Ca-Ti ore type/anti-perovskite type ABO3 electrolyte, wherein A
=Ca, Sr, La；B=Al, Ti, ionic conductivity is in 10-7~10-3, the Li1.5Al0.5Ge1.5P3O12/ of NASICON type
Li1.3Al0.3Ti1.7P3O12, LAGP/LATP, 10-4~10-3S cm-1, Li7La3Zr2O12, the LLZO of carbuncle type,
10-4~10-3S cm-1 and sulphur system electrolyte 10-4~10-2S cm-1.
Preferably, photo-thermal anode can be metal Al, Ru, Au, Ag, Cu, Ni, Co with plasma effect
The composite wood of carbon and positive electrode active material is assembled in by the method for physical vapour deposition (PVD) or chemical deposition Deng/metal oxide RuO2
The photo-thermal anode of plasma enhancing is formed on material.It is also possible to directly turn the carbon of effect with efficient light absorption and with light
One or both of material carbon black, acetylene black, SP, graphene, carbon nanotube, Ketjen black, carbon nano-fiber etc. or more
It is compound with active material and adhesive is combined photo-thermal anode.For lithium-gas cell, can also be directly in solid state electrolysis
The photo-thermal of matter on piece depositing metallic nanoparticles or carbon material anode.
Preferably, photo-thermal negative current collector includes but is not limited to by carbon black, acetylene black, SP, graphene Graphene, carbon
The carbon materials such as nanotube CNT, Ketjen black, carbon nano-fiber, the metals such as aluminium Al, ruthenium Ru, gold Au, silver Ag, copper Cu, nickel, cobalt Co
Material and respective metal oxide, silicon Si, germanium Ge, tin Sn, titanium dioxide TiO2One or both of equal semiconductor materials and
The two or more nano materials being combined.When illumination, which can convert the light to heat to cathode, solid-state
Electrolyte and anode are heated.
Preferably, the photo-thermal negative current collector, can also be by independent optothermal material and negative pole currect collecting bluk recombination
It forms；The optothermal material includes photothermal conversion film, the photothermal conversion film be the metal material nanostructure with it is described
The composite material of one or both of carbon material or more.
Preferably, cathode can be insert type cathode carbon, graphene, TiO2, LiTiO2 etc., alloy type cathode Si, Ge,
Sn, Al etc., conversion cathode (one of Fe2O3, CuO, CoO2 etc. or two kinds or more it is compound.
Solar energy optical-thermal lithium ion battery of the invention, including but not limited to traditional lithium-ion electric based on organic liquid
Pond, lithium-gas cell, solid-state/all-solid lithium-ion battery, solid-state/all solid state lithium-sulfur cell, solid-state/all solid lithium-air
Battery, solid-state/all solid lithium-carbon dioxide battery, solid-state/all solid lithium-nitrogen battery and molten salt electrolyte battery and lithium-gas
Associated batteries extremely hybrid type battery including battery etc..
At low temperature, which is come effectively by design photo-thermal anode Fig. 1 a, 1b or photo-thermal negative current collector Fig. 1 c, 1d
Capture sunlight simultaneously converts thereof into heat and passes to including electrolyte/solid electrolyte, the institute including electrode material and collector
There is battery component.Even so that entire battery be also able to maintain under extremely low temperature external environment a higher operating temperature with
Good cycle performance.At room temperature, the heat that light generates enables to battery to be maintained at a working environment at higher temperature, improves
Charge stores and transmits in battery, can effectively improve the capacity/energy density and cycle performance of battery.
Present embodiment discloses a kind of all solid state lithium-air battery of the solar energy optical-thermal based on LAGP solid electrolyte, systems
Preparation Method including the following steps:
The first step, by GeO2、Li2CO3、Al2O3And NH4H2PO4Powder it is mixed according to mass percent 0.7:0.3:1.8:4
It closes, ball milling and annealing repeatedly for three times, gained powder is pressed into the LAGP solid electrolyte disk that diameter is 1.6cm, by LAGP
Solid electrolyte disk is stand-by in 900 ° of sanding and polishings after re-annealing 1 hour；
Second step, by RuO2, LAGP powder and CNT be added after mixing according to the ratio of mass percent 10:100:1 and bond
Agent 5%, suitable N-Methyl pyrrolidone being added solution being spin-coated on LAGP solid electrolyte on piece after mixing evenly can obtain
To the solid electrolyte piece for being prepared with photo-thermal anode；
Third step, under an ar atmosphere 500 DEG C of annealing 15min；
4th step, from top to bottom by aluminium net plus plate current-collecting body, be coated with LAGP solid electrolyte piece, the lithium metal of photo-thermal anode
Cathode and copper foil negative current collector use aluminum plastic film to be packaged into soft-package battery.
It is work of all solid state lithium-air battery of solar energy optical-thermal of the LAGP solid electrolyte under limiting temperature below
Performance test:
Fig. 2 a is cycle performance of all solid state lithium-air battery of photo-thermal in -78 DEG C to -73 DEG C environment of dry ice；Scheme (2b)
The temperature stablized in dry ice in -78 DEG C to -73 DEG C all solid state photo-thermal cell each section components changes with light application time.
By all-solid-state battery known to Fig. 2 a -78 DEG C at a temperature of illustrate outstanding cycle performance, photo-thermal anode
Pass through capture sunlight and be converted into heat and be heated to 70 DEG C come the ultralow temperature inside battery from -78 DEG C, illustrates effectively
Light heating effect.Thus internal temperature of battery is further dropped to 20 DEG C reported in the literature and less, the photo-thermal that we use is complete
The external work environment temperature of solid state battery can be further decreased from -78 DEG C.In addition the insulation of current maturation and light condensing technology are real
Existing all-solid-state battery is feasible in -200 DEG C of operation.The Ye of such as University Of Tianjin, Adv.Energy
Mater.2017,7,1601657 reports Ru nanometers and is used as photo-thermal catalyst reduction CO2Work, received in Xe light irradiation Ru
Surface temperature of the rice grain on different carriers is up to 280 DEG C to 350 DEG C.The Chen etc., Nature of Massachusetts science and engineering
Energy.2016,16126 propose the concept of heat accumulation, and realize the lower 100 DEG C of water of a sun by foam of polymers and steam
Stripping temperature.
In addition to the implementation, the present invention can also have other embodiments.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (10)
1. the solar energy optical-thermal lithium battery that can be worked in temperature range limit, it is characterised in that: the solar energy optical-thermal lithium battery
For closed lithium ion battery or semi open model lithium ion battery；
The closed lithium ion battery: from top to bottom successively include plus plate current-collecting body, photo-thermal anode, electrolyte, cathode and
Negative current collector；It or from top to bottom successively include plus plate current-collecting body, anode, electrolyte, cathode and photo-thermal negative current collector；Or according to
Secondary includes plus plate current-collecting body, photo-thermal anode, electrolyte, cathode and photo-thermal negative current collector；
The semi open model lithium ion battery: from top to bottom successively include porous current collector, photo-thermal anode, electrolyte, cathode with
And negative current collector；It or from top to bottom successively include porous current collector, anode, electrolyte, cathode and photo-thermal negative current collector；Or
It from top to bottom successively include porous current collector, photo-thermal anode, electrolyte, cathode, photo-thermal negative current collector；
When illumination is irradiated from positive side, photo-thermal anode can capture sunlight and convert thereof into heat to improve entire battery
The temperature of the inside of component, so as to work in the low temperature environment of pole；
When illumination is irradiated from cathode side, photo-thermal negative current collector absorbs sunlight and converts thereof into heat to be transmitted through cathode
To electrolyte and anode, to reach the heating of the component to entire battery, it is made to work in the low temperature environment of pole；
When light is irradiated from anode and cathode simultaneously, photo-thermal anode and photo-thermal negative pole currect collecting physical efficiency capture sunlight simultaneously and will
It is converted into heat to heat entire battery component, it is made effectively to work in the low temperature environment of pole.
2. the solar energy optical-thermal lithium battery according to claim 1 that can be worked in temperature range limit, it is characterised in that: institute
State extremely low temperature environment temperature >=-200oC, the closed lithium ion battery are solid lithium battery, operating temperature range
It is -200oC~200℃；The semi open model lithium ion battery is lithium-gas cell, can be in the extremely low temperature -200 that worksoC environment
Lower work.
3. the solar energy optical-thermal lithium battery according to claim 2 that can be worked in temperature range limit, it is characterised in that: when
The closed lithium ion battery is followed successively by plus plate current-collecting body, photo-thermal anode, electrolyte, cathode and negative pole currect collecting from top to bottom
When body structure, then the upper surface of described plus plate current-collecting body is equipped with optical window；When the closed lithium ion battery from top to bottom according to
It is secondary for plus plate current-collecting body, anode, electrolyte, cathode and when photo-thermal negative current collector, then under the photo-thermal negative current collector
Face is equipped with optical window；When the closed lithium ion battery is followed successively by plus plate current-collecting body, photo-thermal anode, electrolysis from top to bottom
When matter, cathode and photo-thermal negative current collector, then it is all provided with below the upper surface of described plus plate current-collecting body and photo-thermal negative current collector
There is optical window；When the semi open model lithium-gas cell be followed successively by from top to bottom porous anode collector, anode, electrolyte,
When cathode and photo-thermal negative current collector, then optical window is equipped with below the photo-thermal negative current collector；When described semi-open
Formula lithium-gas cell is followed successively by porous anode collector, photo-thermal anode, electrolyte, cathode and photo-thermal cathode collection from top to bottom
When fluid, then optical window is equipped with below the photo-thermal negative current collector.
4. the solar energy optical-thermal lithium battery according to claim 1 that can be worked in temperature range limit, it is characterised in that: institute
State anode be by mass percent be 5% ~ 90% cobalt acid lithium, LiMn2O4, LiFePO4 or ternary material, 5% ~ 95% lithium salts,
The lithium ion cell positive that 3% ~ 50% conductive agent and 3% ~ 15% binder are combined；
Or, by the sulphur active matter of mass percent 5% ~ 85%, 3% ~ 50% conductive agent and the lithium-that is combined of 3% ~ 15% binder
Sulphur cell positive electrode；
Or, by the electronic conductor of mass percent 3% ~ 95%, 3% ~ 95% ionic conductivity electrolyte powder and 3% ~ 100% urge
The lithium that agent is combined-gas cell anode.
5. the solar energy optical-thermal lithium battery according to claim 4 that can be worked in temperature range limit, it is characterised in that: institute
Stating electrolyte is one in liquid organic electrolyte, solid electrolyte, molten salt electrolyte, ionic liquid electrolyte and lithium salts
Kind or two kinds or more of combination.
6. the solar energy optical-thermal lithium battery according to claim 5 that can be worked in temperature range limit, it is characterised in that: institute
Stating solid electrolyte includes but is not limited to Ca-Ti ore type/anti-perovskite type ABO3 electrolyte, wherein A=Ca, Sr, La; B=
Al, Ti, ionic conductivity is in 10-7 ~ 10-3, the Li1.5Al0.5Ge1.5P3O12/ of NASICON type
Li1.3Al0.3Ti1.7P3O12, LAGP/LATP, 10-4 ~ 10-3 S cm-1, the Li7La3Zr2O12 of carbuncle type,
LLZO, 10-4 ~ 10-3 S cm-1 and sulphur system electrolyte 10-4 ~ 10-2 S cm-1.
7. the solar energy optical-thermal lithium battery according to claim 6 that can be worked in temperature range limit, it is characterised in that: institute
Stating photo-thermal anode is the metal or metal oxide RuO that will have plasma effect2It is heavy by physical vapour deposition (PVD) or chemistry
Long-pending method is assembled in the photo-thermal anode that plasma enhancing is formed on the composite material of carbon and positive electrode active material；
Or the carbon material, active material and adhesive that turn effect with efficient light absorption and light are directly being combined photo-thermal just
Pole；
Or directly in the photo-thermal of solid electrolyte on piece depositing metallic nanoparticles or carbon material anode.
8. the solar energy optical-thermal lithium battery according to claim 1 that can be worked in temperature range limit, it is characterised in that: institute
Stating photo-thermal negative current collector includes but is not limited to by carbon black, acetylene black, SP, graphene Graphene, carbon nanotube CNT, section's qin
Black or carbon nano-fiber, aluminium, ruthenium, gold, silver, copper, nickel or cobalt metal material and respective metal oxide, silicon, germanium, tin or dioxy
Change one or both of titanium semiconductor material and the two or more nano materials being combined.
9. the solar energy optical-thermal lithium battery according to claim 8 that can be worked in temperature range limit, it is characterised in that: institute
Photo-thermal negative current collector is stated, is combined by independent optothermal material and negative current collector；The optothermal material includes photo-thermal
Film is converted, the photothermal conversion film is one or both of the nanostructure of the metal material and described carbon material or more
Composite material.
10. one kind can temperature range limit work solar energy optical-thermal lithium battery preparation method, it is characterised in that: it is described too
Positive energy photo-thermal lithium battery is all solid state lithium-air battery of solar energy optical-thermal based on LAGP solid electrolyte, and preparation method includes
Following steps:
The first step, by GeO2、 Li2CO3、 Al2O3And NH4H2PO4Powder according to mass ratio 0.7:0.3:1.8:4 mix,
Gained powder is pressed into LAGP solid electrolyte disk, LAGP solid electrolyte disk is existed by ball milling and annealing repeatedly for three times
900 ° of sanding and polishings after re-annealing 1 hour are stand-by；
Second step, by RuO2, LAGP powder and CNT binder is added after mixing according to the ratio of mass percent 10:100:1
5%, suitable N-Methyl pyrrolidone is added solution is spin-coated on LAGP solid electrolyte on piece after mixing evenly can be obtained system
Have the solid electrolyte piece of photo-thermal anode；
Third step, under an ar atmosphere 500o15 min of C annealing；
4th step, from top to bottom by aluminium net plus plate current-collecting body, be coated with LAGP solid electrolyte piece, the lithium anode of photo-thermal anode
And copper foil negative current collector is packaged into soft-package battery using aluminum plastic film.
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