CN105098140B - Liquid metal negative material and room temperature liquid metal battery, preparation method and purposes - Google Patents

Liquid metal negative material and room temperature liquid metal battery, preparation method and purposes Download PDF

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Publication number
CN105098140B
CN105098140B CN201410383865.0A CN201410383865A CN105098140B CN 105098140 B CN105098140 B CN 105098140B CN 201410383865 A CN201410383865 A CN 201410383865A CN 105098140 B CN105098140 B CN 105098140B
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liquid metal
charge
battery
ether
room temperature
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CN105098140A (en
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胡勇胜
余觉知
褚赓
李泓
黄学杰
陈立泉
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of liquid metal negative material and room temperature liquid metal battery, preparation method and purposes, described negative material is the blackish green liquid that alkali metal, aromatic compound and ether solvent mixing generate；Wherein, any one during described alkali metal is metallic sodium, lithium metal or metallic potassium；Described aromatic compound is any one in the derivant of biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene；Described ether solvent includes one or more in glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether etc..

Description

Liquid metal negative material and room temperature liquid metal battery, preparation method and purposes
Technical field
The present invention relates to field of material technology, particularly relate to a kind of liquid metal negative material and room temperature liquid Metal battery, preparation method and purposes.
Background technology
Along with the environmental problem that is day by day exhausted and that bring of traditional fossil energy becomes increasingly conspicuous, develop too The regenerative resources such as sun energy, wind energy are extremely urgent.But, due to solar energy, the undulatory property of wind energy and Having a rest property result in the instability of electrical network, so needing to greatly develop extensive energy storage technology.Extensive energy storage Technology can effectively solve the problem that the regenerative resource intermittence such as solar energy, wind energy is powered, it is achieved needs Ask management, eliminate peak-valley difference, smooth load etc. round the clock.
Extensive energy storage technology currently mainly has water-storage, compressed-air energy storage, flywheel energy storage, electricity Chemical energy storage etc..Various energy storage technologies have respective use condition and advantage, all in positive research and development With the demonstration stage.Wherein energy storage electrochmical power source such as sodium-sulphur battery, all-vanadium flow battery, lithium ion battery Some have been had to demonstrate as extensive energy storage device.
But sodium-sulphur battery needs to run under 300 degree of high temperature, molten metal sodium and the directly use of sulfur Result in this battery and there is serious etching problem and potential safety hazard.Used by all-vanadium flow battery Vanadium ion belongs to extremely toxic substance and resource-constrained, additionally there is both positive and negative polarity active substance in its running The problem of phase counterdiffusion, and the energy density of this energy-storage battery is the highest.Lithium ion battery conduct Extensive energy-storage battery has preferable performance, but the manufacturing cost of lithium-ion energy storage battery is high.Therefore It is comprehensive that a kind of energy-storage battery can meet low cost, good, the abundant raw materials of safety etc. The requirement of property.
Summary of the invention
Embodiments provide a kind of liquid metal negative material and room temperature liquid metal battery, preparation Method and purposes.Described liquid metal negative material have the mobility of liquid, good electronic conduction and Ionic conductivity, low current potential, high safety and good wetting property, make this material The battery being prepared as negative pole has the characteristic of high-energy-density, long circulation life, can be used for solar energy, The storage of the power station output electric energy such as wind energy.
First aspect, embodiments providing a kind of negative material is alkali metal, aromatic compound The blackish green liquid generated with ether solvent mixing；
Wherein, any one or more during described alkali metal is metallic sodium, lithium metal or metallic potassium；
Described aromatic compound is biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene Any one or more in derivant；
Described ether solvent includes ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrem Glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl-butyl ether, butyl oxide, diamyl ether, isoamyl ether, Two hexyl ethers, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-bis- Oxygen Pentamethylene., dimethoxymethane, 1,2-dimethoxy propane, dioxolane, Isosorbide-5-Nitrae-dioxane, Oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide, sulfolane or dimethyl sulfone In any one or more.
Second aspect, embodiments provides a kind of liquid metal as described in above-mentioned first aspect and bears The preparation method of pole material, described method includes:
In the protective atmosphere of argon, alkali metal and aromatic compound are added ether according to certain mol proportion In kind solvent, stand, obtain described liquid metal negative material；
Wherein, any one or more during described alkali metal is metallic sodium, lithium metal or metallic potassium；
Described aromatic compound is biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene Any one or more in derivant；
Described ether solvent includes ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrem Glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl-butyl ether, butyl oxide, diamyl ether, isoamyl ether, Two hexyl ethers, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-bis- Oxygen Pentamethylene., dimethoxymethane, 1,2-dimethoxy propane, dioxolane, Isosorbide-5-Nitrae-dioxane, Oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide, sulfolane or dimethyl sulfone In any one or more.
The third aspect, embodiments provides a kind of liquid metal comprised described in above-mentioned first aspect Negative material can charge and discharge room temperature liquid metal battery.
Preferably, described can also include by charge and discharge room temperature liquid metal battery:
One in liquid positive electrode or slurry positive electrode, and the consolidating of ionic conduction, electronic isolation Body dielectric film；
Wherein, described solid electrolyte includes for conducts sodium ions, lithium ion or potassium ion Na3Zr2Si2PO12Pottery, Na-β "-Al2O3Pottery, K-β "-Al2O3Pottery, Li7La3Zr2O12Pottery or Li10GeP2S12Any one in pottery.
Preferably, the preparation method of described slurry positive electrode includes:
The pressed powder of positive active material, carbon dust are pressed certain mass than mix homogeneously, add a certain amount of Supporting electrolyte and be stirred, i.e. obtain described liquid positive electrode；
Wherein, described positive active material includes: Na0.44MnO2、NaTi2(PO4)3、Na3V2(PO4)3、 Na0.8Li0.1Ni0.25Mn0.65O2、NaMg0.1Ni0.4Mn0.2Ti0.3O2, S, K3Fe(CN)6、Na4Fe(CN)6、FePO4 In any one or more.
Preferably, the preparation method of described slurry positive electrode includes:
Liquid positive electrode, carbon dust are pressed certain mass than mix homogeneously, add and a certain amount of support electrolysis Matter is also stirred, and i.e. obtains described liquid positive electrode.
It is further preferred that described liquid positive electrode is:
With 1,4-benzoquinone, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, acenaphthenequinone derivative In the derivant of thing, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, with glycol dimethyl ether, carbon Acid propylene ester, tetraethyleneglycol dimethyl ether, dimethylformamide or N-Methyl pyrrolidone any one or more It is mixed into solvent, the liquid of composition.
It is further preferred that the preparation method of described liquid positive electrode includes:
1,4-benzoquinone with 0.1～5mol, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, In the derivant of the derivant of acenaphthenequinone, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, is dissolved in 1L With glycol dimethyl ether, Allyl carbonate, tetraethyleneglycol dimethyl ether, dimethylformamide or N-methyl In the solvent of any one or more mixing of ketopyrrolidine, add a certain amount of supporting electrolyte, i.e. obtain institute State liquid positive electrode.
It is further preferred that described liquid positive electrode is:
In benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene arbitrary as solute, with glycol dimethyl ether, Diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethylformamide or N-Methyl pyrrolidone any one Or the multiple solvent that is mixed into, the liquid of composition.
It is further preferred that the preparation method of described liquid positive electrode includes:
Any one or more mixing in benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene with 0.1～5mol For solute, be dissolved in the glycol dimethyl ether of 1L, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, two In methylformamide or any one or more mixed solvent of N-Methyl pyrrolidone, add a certain amount of alkali gold Belong to, stand, i.e. obtain described liquid positive electrode.
It is further preferred that described liquid positive electrode is:
With Na2SxFor solute, with dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, two Methylformamide, N-Methyl pyrrolidone or water any one or more be mixed into solvent constitute solution；Its In, 3≤x≤12.
It is further preferred that the preparation method of described liquid positive electrode includes:
According to Na2The mol ratio of S/S=1/ (x-1) is by Na2S Yu S adds dimethyl sulfoxide, diethylene glycol two In methyl ether, tetraethyleneglycol dimethyl ether or dimethylformamide or N-Methyl pyrrolidone or the arbitrary solvent of water, And add a certain amount of supporting electrolyte stir to being completely dissolved, i.e. obtain described liquid positive electrode；
Wherein, 3≤x≤12.
Can charge and discharge room temperature liquid metal battery be cylindrical battery it is further preferred that described, including:
Stainless Steel Shell and solid electrolyte tube；
Described solid electrolyte tube is contactless to be nested in described stainless steel case body, described Stainless Steel Shell Confined space between inwall and described solid electrolyte tube outer wall is used for housing described liquid positive electrode； It is used in described solid electrolyte tube housing described liquid metal negative material.
Can charge and discharge room temperature liquid metal battery be double flow battery it is further preferred that described, including:
Battery container, solid electrolyte film, positive pole fluid reservoir, negative pole fluid reservoir and two pumps；
Described battery container is divided into airtight positive pole space and negative pole space by described solid electrolyte film, Wherein said positive pole space is connected with described positive pole fluid reservoir, by a pump by accommodating in positive pole fluid reservoir Described liquid positive electrode pump in described positive pole space, described negative pole space and described negative pole fluid reservoir It is connected, described liquid metal negative material accommodating in negative pole fluid reservoir is pumped into described negative by a pump In space, pole.
Can charge and discharge room temperature liquid metal battery be single flow battery it is further preferred that described, including:
Battery container, solid electrolyte film, positive pole fluid reservoir and pump；
Described battery container is divided into airtight positive pole space and negative pole space by described solid electrolyte film, Wherein said positive pole space is connected with described positive pole fluid reservoir, by described pump by accommodating in positive pole fluid reservoir Described liquid positive electrode pump in described positive pole space, described negative pole space is used for housing described liquid Metal negative electrode material.
Can charge and discharge room temperature liquid metal battery be flat metal battery it is further preferred that described, including:
Battery container and solid electrolyte film；
Described battery container is divided into airtight positive pole space and negative pole space by described solid electrolyte film, Described positive pole space is used for housing described liquid positive electrode, and described negative pole space is used for housing described liquid Metal negative electrode material.
Fourth aspect, embodiments provide a kind of as described in the above-mentioned third aspect can charge and discharge room temperature The purposes of liquid metal cell, described can charge and discharge room temperature liquid metal battery for solar electrical energy generation, wind-force Generating, intelligent grid peak regulation, distribution power station, back-up source or the extensive energy storage device of communication base station.
The liquid metal negative material that the embodiment of the present invention provides has the mobility of liquid, good electronics Conduction and ionic conductivity, low current potential, high safety and good wetting property, with low cost, Rich material resources, has high-energy-density, long circulating longevity using this material as the battery that negative pole is prepared as The characteristic of life, can be used for the storage of the power station such as solar energy, wind energy output electric energy.
Accompanying drawing explanation
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
The electrochemistry resistance of the biphenyl-DME-metallic sodium liquid metal negative pole that Fig. 1 provides for the embodiment of the present invention 2 Anti-spectrogram；
Molten after the biphenyl-DME-metallic sodium solution dropping deionized water that Fig. 2 provides for the embodiment of the present invention 2 Liquid changes over figure；
The dissolubility signal of the biphenyl-DME-metallic sodium liquid negative pole that Fig. 3 provides for the embodiment of the present invention 2 Figure；
The structural representation of the cylindrical battery that Fig. 4 provides for the embodiment of the present invention；
The structural representation of the double flow battery that Fig. 5 provides for the embodiment of the present invention；
The structural representation of the single flow battery that Fig. 6 provides for the embodiment of the present invention；
The structural representation of the flat metal battery that Fig. 7 provides for the embodiment of the present invention；
The liquid negative material that Fig. 8 provides for the embodiment of the present invention 9 and anthraquinone liquid positive electrode institute structure Front ten weeks charge-discharge performance curves of the battery made；
The liquid metal negative material that Fig. 9 provides for the embodiment of the present invention 9 and anthraquinone liquid positive electrode The cycle performance of battery curve constructed；
The liquid metal negative material that Figure 10 provides for the embodiment of the present invention 10 and anthraquinone-white carbon black slurry positive pole The charge-discharge performance curve of the battery constructed；
The liquid metal negative material that Figure 11 provides for the embodiment of the present invention 11 and benzoquinone liquid positive electrode First three week charge-discharge performance curve of the battery constructed；
The liquid metal negative material that Figure 12 provides for the embodiment of the present invention 12 and acenaphthenequinone liquid positive electrode The battery charging and discharging performance curve constructed；
Anthraquinone-PC-sodium perchlorate that Figure 13 provides for the embodiment of the present invention 12, benzoquinone-PC-sodium perchlorate, Acenaphthenequinone-PC-sodium perchlorate is first all discharge and recharge comparison diagrams of liquid positive electrode；
Liquid metal negative material that Figure 14 provides for the embodiment of the present invention 13 and NaTi2(PO4)3Constructed The charge-discharge performance curve of battery；
Liquid metal negative material that Figure 15 provides for the embodiment of the present invention 13 and NaTi2(PO4)3Constructed The cycle performance curve of battery；
Liquid metal negative material that Figure 16 provides for the embodiment of the present invention 14 and Na3V2(PO4)3Constructed The charge-discharge performance curve of battery；
Liquid metal negative material that Figure 17 provides for the embodiment of the present invention 15 and Na0.44MnO2The electricity of structure The charge-discharge performance curve in pond；
The liquid metal negative material that Figure 18 provides for the embodiment of the present invention 16 and pyrene-DME liquid positive pole group The battery charging and discharging performance curve become；
The liquid metal negative material that Figure 19 provides for the embodiment of the present invention 17 is with aphthacene-DME liquid just The battery charging and discharging performance curve of pole composition；
Liquid metal negative material that Figure 20 provides for the embodiment of the present invention 18 and Na2S8Liquid positive pole forms Battery charging and discharging performance curve；
After the many sulphions of dropping that Figure 21 provides for the embodiment of the present invention 18 biphenyl-DME-metallic sodium solution with The variation diagram of time；
Liquid metal negative material that Figure 22 provides for the embodiment of the present invention 19 and Na2S12Liquid positive pole forms Battery charging and discharging performance curve；
The liquid metal negative material that Figure 23 provides for the embodiment of the present invention 20 and S-white carbon black slurry positive pole institute The battery of structure charge-discharge performance curve between 1.5～2.7V；
The liquid metal negative material that Figure 24 provides for the embodiment of the present invention 20 and S-white carbon black slurry positive pole institute The battery of structure charge-discharge performance curve between 1.7～2.8V；
The liquid metal negative material that Figure 25 provides for the embodiment of the present invention 21 and tetramethoxy piperidines liquid The charge-discharge performance curve of the battery that positive pole is constructed；
Liquid metal negative material that Figure 26 provides for the embodiment of the present invention 22 and K3Fe(CN)6Aqueous solution institute The charge-discharge performance curve of the battery of structure；
The liquid metal negative material that Figure 27 provides by the embodiment of the present invention 23 and benzophenone are constructed The charge-discharge performance curve of battery；
The liquid metal negative material that Figure 28 provides by the embodiment of the present invention 24 is constructed with iodine liquid positive pole The charge-discharge performance curve of battery；
The liquid metal negative material that Figure 29 provides for the embodiment of the present invention 25 and ferrocene liquid positive pole institute The charge-discharge performance curve of the battery of structure；
The liquid metal negative material that Figure 30 provides by the embodiment of the present invention 26 is constructed with acenaphthene liquid positive pole The charge-discharge performance curve of battery；
The liquid metal negative material that Figure 31 provides for the embodiment of the present invention 27 and quinoline woods liquid positive pole institute The charge-discharge performance curve of the battery of structure；
Naphthalene-DME-metallic sodium liquid the negative pole that Figure 32 provides for the embodiment of the present invention 28 and anthraquinone-PC-height chlorine The battery charging and discharging performance curve of acid sodium liquid positive pole composition；
Biphenyl-DME-the metallic sodium that Figure 33 provides for the embodiment of the present invention 29 and excess anthraquinone solution composition Battery charging and discharging curve；
The pictorial diagram of the cylindrical battery that Figure 34 provides for the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended to limit this The protection domain of invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of liquid metal negative material.
Wherein, described negative material is the ink that alkali metal, aromatic compound and ether solvent mixing generate Green liquid；
Concrete, described alkali metal can be metallic sodium (Na), lithium metal (Li) or metallic potassium (K) In any one or more mixing；
Described aromatic compound can be biphenyl (BP), connection benzene derivate, naphthalene (NP), naphthalene Any one or more mixing in the derivant of derivant, anthracene or anthracene；
Wherein；Connection benzene derivate is specifically as follows: biphenyl, DCBP, tetrachloro biphenyl three Benzene, x-methyl biphenyl, x-ethyl biphenyl etc.；
Naphthalene derivatives is specifically as follows: phenanthrene, dichloronaphtalene, Tetrachloronaphthalene, x-methyl naphthalene, Isosorbide-5-Nitrae-diformazan Base naphthalene, x-ethylnaphthalene.
Described ether solvent includes ether, methyl ether, glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), tetraethyleneglycol dimethyl ether (TEGDME), dipropyl ether, diisopropyl ether, ethyl-butyl ether, Butyl oxide, diamyl ether, isoamyl ether, two hexyl ethers, oxolane, 2-methyltetrahydrofuran, 1,3-bis- Oxygen Pentamethylene., 4-methyl-1,3-dioxy Pentamethylene., dimethoxymethane, 1,2-dimethoxy propane, Dioxolane, Isosorbide-5-Nitrae-dioxane, oxirane, expoxy propane, 1,1-diethoxyethane, two Any one or more mixing in methyl sulfoxide, sulfolane or dimethyl sulfone.Wherein it is preferably, DME, One in DEGDME or TEGDME.
Alkali metal, aromatic compound react after mixing in ether solvent, below with sodium, biphenyl Illustrate as a example by mixing with DME solvent.
Course of reaction is as shown in following formula 1:
Table 1 below gives the liquid that distinct fragrance compounds of group generates in DME solvent with metallic sodium State metal negative electrode properties of materials.
Table 1
The liquid metal negative material that the embodiment of the present invention provides has the mobility of liquid, good electricity Electronic conduction and ionic conductivity, low current potential, high safety and good wetting property, cost Cheap, rich material resources, this material is had high-energy-density, long circulating longevity as battery cathode The characteristic of life.
Embodiment 2
The embodiment of the present invention 2 provides a kind of liquid metal negative material as described in above-described embodiment 1 Preparation method.Described method includes: in the protective atmosphere of argon, by alkali metal and aromatic series Compound adds in ether solvent according to certain mol proportion, stands, obtains described liquid metal negative material.
Concrete, described alkali metal can be metallic sodium (Na), lithium metal (Li) or metallic potassium (K) In any one or more mixing；
Described aromatic compound can be biphenyl (BP), connection benzene derivate, naphthalene (NP), naphthalene Derivant, anthracene or anthracene derivant in any one or more mixing；
Wherein；Connection benzene derivate is specifically as follows: biphenyl, DCBP, tetrachloro biphenyl three Biphenyl, x-methyl biphenyl, x-ethyl biphenyl etc.；
Naphthalene derivatives is specifically as follows: phenanthrene, dichloronaphtalene, Tetrachloronaphthalene, x-methyl naphthalene, Isosorbide-5-Nitrae-two Methyl naphthalene, x-ethylnaphthalene.
Described ether solvent includes ether, methyl ether, glycol dimethyl ether (DME), diethylene glycol two Methyl ether (DEGDME), tetraethyleneglycol dimethyl ether (TEGDME), dipropyl ether, diisopropyl ether, ethyl Butyl ether, butyl oxide, diamyl ether, isoamyl ether, two hexyl ethers, oxolane, 2-methyl tetrahydrochysene furan Mutter, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, dimethoxymethane, 1,2- Dimethoxy propane, dioxolane, Isosorbide-5-Nitrae-dioxane, oxirane, expoxy propane, 1,1- Any one or more mixing in diethoxyethane, dimethyl sulfoxide, sulfolane or dimethyl sulfone. Wherein it is preferably, the one in DME, DEGDME or TEGDME.
Below, carry out specifically as a example by the preparation process of biphenyl-DME-metallic sodium liquid metal negative pole Bright.
In the glove box of full Ar gas, the ratio of 1:1 weighs metallic sodium 0.23g, biphenyl in molar ratio 1.54g puts in same 20ml weighing botle stand-by.10mL ethylene glycol is taken afterwards with 10ml liquid-transfering gun Dimethyl ether (DME) liquid is injected in the weighing botle being placed with metallic sodium, biphenyl, and now solution becomes rapidly Become blackish green.The blackish green solution left standstill obtained i.e. be can get for 2 hours the liquid of biphenyl-DME-metallic sodium State metal negative electrode.Fig. 1 is the electrochemical impedance spectroscopy of above-mentioned biphenyl-DME-metallic sodium liquid metal negative pole Figure, can be seen that from figure resistance is 86 ohm when concentration is 1mol/l.By Conductivity formula σ =k/R can be calculated σ1mol/l=1.2x10-2S/cm, our test simultaneously obtains 1mol/l biphenyl The conductivityσ of-DME-lithium metal1mol/l=1.1x10-2S/cm.Above-mentioned biphenyl-DME-metallic sodium liquid gold Belong to negative pole safety experiment to be illustrated by Fig. 2, the metallic sodium solution of biphenyl-DME-shown in figure dropping deionization Solution after water changes over figure.The anti-of biphenyl-DME-metallic sodium solution and water is can be seen that from figure Should not have as metallic sodium and water react violent, illustrate that biphenyl-DME-metallic sodium solution is used as negative pole Security performance higher than metallic sodium negative pole.The solubility experiment of above-mentioned biphenyl-DME-metallic sodium liquid negative pole Illustrated by Fig. 3, from figure, can be seen that the dissolubility of biphenyl-DME-metallic sodium, more than 5mol/l, is pressed Specific capacity 151mAh/g according to biphenyl-DME-metallic sodium calculates, and obtains the volume of biphenyl-DME-metallic sodium Specific capacity is 1.4x102Ah/L, high dissolubility can obtain high volume energy density.Need explanation , concentration of the present invention is all calculated by biphenyl concentration, and wherein biphenyl rubs with alkali-metal Your ratio is 1:1, but this ratio is only for illustrating the present invention in an embodiment, and the ratio of the present invention Example scope is not limited thereto ratio.
Embodiment 3
The embodiment of the present invention additionally provide a kind of liquid metal negative material can charge and discharge room temperature liquid gold Belong to battery.The negative material of described battery is the liquid metal negative material described in above-described embodiment 1, Can be prepared by the method described in above-described embodiment 2.
Additionally, the present embodiment provide can also include by charge and discharge room temperature liquid metal battery:
One in liquid positive electrode or slurry positive electrode, and ionic conduction, electronic isolation Solid electrolyte film；
Wherein, described solid electrolyte includes for conducts sodium ions, lithium ion or potassium ion Na3Zr2Si2PO12Pottery, Na-β "-Al2O3Pottery, K-β "-Al2O3Pottery, Li7La3Zr2O12Pottery or Li10GeP2S12Any one in pottery.
Respectively liquid positive electrode or slurry positive electrode will be entered respectively with embodiment 4-8 respectively below Row explanation.
Embodiment 4
The embodiment of the present invention 4 in order to a kind of liquid positive electrode described in above-described embodiment 3 to be described, and Its preparation method.
Described liquid positive electrode is:
With 1,4-benzoquinone, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, acenaphthenequinone derivative In the derivant of thing, phenanthrenequione or phenanthrenequione arbitrary for solute, with glycol dimethyl ether, Allyl carbonate or four Glycol dimethyl ether is arbitrary for solvent, the liquid of composition.
Its preparation method can be:
1,4-benzoquinone with 0.1～5mol, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, In the derivant of the derivant of acenaphthenequinone, phenanthrenequione or phenanthrenequione arbitrary for solute, be dissolved in 1L with ethylene glycol bisthioglycolate In the arbitrary solvent of methyl ether, Allyl carbonate or tetraethyleneglycol dimethyl ether, add a certain amount of supporting electrolyte, I.e. obtain described liquid positive electrode.
Such as in a specific example, as a example by anthraquinone-PC-sodium perchlorate liquid positive electrode, its Concrete preparation process is:
Weigh anthraquinone 2.08g and be dissolved in the PC solvent of 10mL, be simultaneously introduced 1.4g trifluoromethyl sulfonate and make For supporting electrolyte, stir to being completely dissolved i.e. available required liquid positive electrode.
Embodiment 5
The embodiment of the present invention 5 in order to a kind of liquid positive electrode described in above-described embodiment 3 to be described, and Its another kind of preparation method.
Described liquid positive electrode is:
In benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene arbitrary as solute, with glycol dimethyl ether, Diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether are arbitrary for solvent, the liquid of composition.
Its preparation method can be:
In benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene with 0.1～5mol arbitrary as solute, dissolve In the arbitrary solvent of glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether of 1L, add A certain amount of alkali metal, stands, i.e. obtains described liquid positive electrode.
Such as in a specific example, as a example by aphthacene-DME-metallic sodium liquid positive electrode, Its concrete preparation process is:
Weigh aphthacene 2.20g and be dissolved in the DME solvent of 10mL, be simultaneously introduced the metallic sodium conduct of 160mg Additive, stirs to being completely dissolved i.e. available required liquid positive electrode.
Embodiment 6
The embodiment of the present invention 6 in order to a kind of liquid positive electrode described in above-described embodiment 3 to be described, and Its another preparation method.
Described liquid positive electrode is:
With Na2SxFor solute, with dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or water Arbitrary solution constituted for solvent；Wherein, 3≤x≤12.
Its preparation method includes:
According to Na2The mol ratio of S/S=1/ (x-1) is by Na2S Yu S adds dimethyl sulfoxide, diethylene glycol two In the arbitrary solvent of methyl ether, tetraethyleneglycol dimethyl ether or water, and add the stirring of a certain amount of supporting electrolyte extremely It is completely dissolved, i.e. obtains described liquid positive electrode；Wherein, 3≤x≤12.
Such as in a specific example, with Na2SxAs a example by-DMSO liquid positive electrode, it is concrete Preparation process is:
According to Na2The mol ratio of S/S=1/ (x-1) weighs appropriate Na2It is sub-that S Yu S joins dimethyl In sulfone (DMSO) solution, it is simultaneously introduced a certain amount of trifluoromethyl sulfonate and stirs as supporting electrolyte Mix to being completely dissolved i.e. available required liquid positive electrode.This liquid positive electrode has well Dissolubility, the Na prepared the most in this approach2S8With Na2S4Dissolubility be all higher than 1mol/L.
Embodiment 7
The embodiment of the present invention 7 is in order to illustrate the one of the slurry positive electrode described in above-described embodiment 3 Preparation method.
By Na0.44MnO2、NaTi2(PO4)3、Na3V2(PO4)3、Na0.8Li0.1Ni0.25Mn0.65O2、 NaMg0.1Ni0.4Mn0.2Ti0.3O2, S, K3Fe(CN)6、Na4Fe(CN)6、FePO4In Deng any one or many Kind of the pressed powder of positive active material, carbon dust press certain mass than mix homogeneously, add a certain amount of Supporting electrolyte is also stirred, and i.e. obtains described liquid positive electrode.
Embodiment 8
The embodiment of the present invention 8 is in order to illustrate another of the slurry positive electrode described in above-described embodiment 3 Plant preparation method.
Any one liquid positive electrode that above-described embodiment 4 or embodiment 5 or embodiment 6 are provided, And carbon dust presses certain mass than mix homogeneously, add a certain amount of supporting electrolyte and be stirred, I.e. obtain described liquid positive electrode.
Below by some specific embodiments, provide the present invention can charge and discharge room temperature liquid metal electricity Preparation method and the performance in pond are described in further detail.
Embodiment 9
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with anthraquinone-PC-sodium perchlorate liquid positive electrode constructed can charge and discharge room temperature liquid metal battery Preparation method, and charge-discharge performance.
Its concrete preparation method is:
1, take the anthraquinone-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected into shown in Fig. 4 Stainless steel case in as positive pole.
2, by ready Na-β "-Al2O3Earthenware is inserted into the rustless steel equipped with liquid positive electrode As electrolyte and barrier film in shell.
3, the liquid metal negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL are taken It is injected into above-mentioned Na-β "-Al2O3As negative pole in earthenware, ready aluminum net is inserted into negative simultaneously Pole liquid is as collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging cuts Only voltage is 2.6V, and charging and discharging currents is 0.4mA.Test result is shown in Fig. 8, and its first all discharge capacity can Reaching 300mAh/g, charging capacity 250mAh/g, first all coulombic efficiencies are about 84%, discharge potential platform It is about 1.75V.Its cycle performance test result is as it is shown in figure 9, test result shows to have circulated 400 After week, discharge capacity keeps 88%.
Embodiment 10
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with anthraquinone-white carbon black slurry positive electrode constructed can the preparation side of charge and discharge room temperature liquid metal battery Method, and charge-discharge performance.
Its concrete preparation method is:
1, weigh anthraquinone 10mg and white carbon black 2mg a certain amount of PC-sodium perchlorate solution of addition to be mixed into It is injected into after slurry the stainless steel case shown in Fig. 4 Nei as positive pole.
2, by ready Na-β "-Al2O3It is stainless that earthenware is inserted into equipped with slurry positive electrode As electrolyte and barrier film in box hat.
3, taking the liquid negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL injects To above-mentioned Na-β "-Al2O3As negative pole in earthenware, ready aluminum net is inserted into negative electrode solution simultaneously Body is as collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.2V, and charging cuts Only voltage is 2.6V, and charging and discharging currents is 1mA.Test result is shown in Figure 10, and its first all discharge capacity can Reaching 320mAh/g, charging capacity 260mAh/g, first all coulombic efficiencies are about 81%.
Embodiment 11
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with benzoquinone-PC-sodium perchlorate liquid positive electrode constructed can charge and discharge room temperature liquid metal battery Preparation method, and charge-discharge performance.
Its concrete preparation method is:
1, take the benzoquinone-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected into shown in Fig. 4 Stainless steel case in as positive pole.
2, by ready Na3Zr2Si2PO12Earthenware is inserted into the rustless steel equipped with liquid positive electrode As electrolyte and barrier film in shell.
3, taking the liquid negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL injects To above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into negative pole simultaneously Liquid is as collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging cuts Only voltage is 2.6V, and charging and discharging currents is 0.4mA.Test result is shown in Figure 11, it can be seen that its head is put in week Capacitance is about 86% up to 260mAh/g, charging capacity 300mAh/g, first all coulombic efficiencies, fill, Discharge potential platform is about 2.4V.
Embodiment 12
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with acenaphthenequinone-PC-sodium perchlorate liquid positive electrode constructed can charge and discharge room temperature liquid metal battery Preparation method, and charge-discharge performance.
Its concrete preparation method is:
1, take the acenaphthenequinone-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected into shown in Fig. 4 Stainless steel case in as positive pole.
2, by ready Na3Zr2Si2PO12Earthenware is inserted into the rustless steel equipped with liquid positive electrode As electrolyte and barrier film in shell.
3, taking the liquid negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL injects To above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into negative pole simultaneously Liquid is as collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging cuts Only voltage is 3V, and charging and discharging currents is 0.4mA.Test result is shown in Figure 12, it can be seen that its first Zhou Fang electricity Capacity is about 88% up to 180mAh/g, charging capacity 160mAh/g, first all coulombic efficiencies, fills, puts Electric potential platform is about 1.9～2.1V.Figure 13 is based on said method, is respectively adopted anthraquinone-PC- Sodium perchlorate, benzoquinone-PC-sodium perchlorate, acenaphthenequinone-PC-sodium perchlorate are the first week of liquid positive electrode Discharge and recharge comparison diagram, can be seen that from figure employing benzoquinone-PC-sodium perchlorate there is higher current potential and The current potential of anthraquinone-PC-sodium perchlorate is relatively low, but can be seen that anthraquinone-PC-height chlorine from above test The cyclical stability of acid sodium is best to have preferable prospect.
Embodiment 13
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with NaTi2(PO4)3Constructed can the preparation method of charge and discharge room temperature liquid metal battery, and fill Discharge performance.
Its concrete preparation method is:
1, by NaTi2(PO4)3Powder and acetylene black, binding agent Kynoar (PVDF) according to The weight ratio mixing of 80:10:10, adds appropriate N-Methyl pyrrolidone (NMP) solvent, often The environment that temperature is dried grinds and forms slurry, then slurry is evenly applied in current collector aluminum foil, dry The pole piece coiling of 60 × 20mm it is cut at Na-β after dry "-Al2O3On earthenware outer wall, insert afterwards In stainless steel shell shown in shown in Fig. 4, and drip the sodium perchlorate of 400mL, Allyl carbonate electrolyte As positive pole.
2, take the biphenyl for preparing, DME, metallic sodium liquid negative material 10mL are injected into above-mentioned Na-β″-Al2O3As negative pole in earthenware, ready aluminum net is inserted into simultaneously negative pole liquid as Collector.
3, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging cuts Being 2.6V to voltage, charging and discharging currents is 0.04mA.Test result is shown in Figure 14, it can be seen that its first week Discharge capacity is about 99% up to 110mAh/g, charging capacity 109mAh/g, first all coulombic efficiencies, fill, Discharge potential platform is about 1.9～2.1V.Its cycle performance test result such as Figure 15, circulate 60 weeks it Its capacity rear keeps 87%.
Embodiment 14
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with Na3V2(PO4)3Constructed can the preparation method of charge and discharge room temperature liquid metal battery, and fill Discharge performance.
Its concrete preparation method is:
1, by Na3V2(PO4)3Powder and acetylene black, binding agent PVDF are according to the weight ratio of 80:10:10 Mixing, add appropriate nmp solvent, in the environment of normal temperature drying grind formed slurry, then Slurry is evenly applied in current collector aluminum foil, and the pole piece coiling being cut into 60 × 20mm after drying exists Na3Zr2Si2PO12On pipe outer wall, insert in stainless steel shell shown in shown in Fig. 4 afterwards, be simultaneously added dropwise 400mL Sodium perchlorate, Allyl carbonate electrolyte is as positive pole.
2, take the biphenyl for preparing, DME, metallic sodium liquid negative material 10mL are injected into above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into this negative pole liquid simultaneously and makees For collector.
3, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 2.8V, and charging cuts Being 3.6V to voltage, charging and discharging currents is 0.04mA.Test result is shown in Figure 16, it can be seen that its head fills in week Capacitance is about 95% up to 115mAh/g, discharge capacity 109mAh/g, first all coulombic efficiencies, fill, Discharge potential platform is about 3.1～3.3V.
Embodiment 15
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with Na0.44MnO2Structure can the preparation method of charge and discharge room temperature liquid metal battery, and discharge and recharge Performance.
Its concrete preparation method is:
1, by Na0.44MnO2Powder mixes according to the weight ratio of 80:10 with white carbon black, is simultaneously introduced appropriate Trifluoromethyl sulfonate, Allyl carbonate supporting electrolyte be mixed into slurry, then slurry is injected As positive pole in stainless steel shell shown in Fig. 4, afterwards by ready Na-β, "-Al2O3 earthenware is inserted Enter to stainless steel shell.
2, take the biphenyl for preparing, DME, metallic sodium liquid negative material 10mL are injected into above-mentioned Na-β″-Al2O3As negative pole in earthenware, ready aluminum net is inserted into simultaneously negative pole liquid as Collector.
3, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 2V, charge by Voltage is 3.8V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 17, it can be seen that its first Zhou Fang electricity Capacity is about 99% up to 110mAh/g, charging capacity 109mAh/g, first all coulombic efficiencies, fills, puts Electric potential scope is 2～3.8V.
Embodiment 16
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with pyrene-DME-metallic sodium liquid positive electrode constructed can the system of charge and discharge room temperature liquid metal battery Preparation Method, and charge-discharge performance.
Its concrete preparation method is:
1, take that the pyrene-DME-metallic sodium liquid positive electrode 10mL prepared is injected into shown in Fig. 4 is stainless As positive pole in box hat.
2, by ready Na-β "-Al2O3Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, taking the liquid negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL, is injected into Above-mentioned Na-β "-Al2O3As negative pole in earthenware, ready aluminum net is inserted into negative pole liquid simultaneously and makees For collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses the charge and discharge mode of limit capacity to carry out, and discharge voltage is 0.45V, is charged to electricity Pressure is 0.6V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 18, it can be seen that its discharge capacity up to 120mAh/g, charging capacity 120mAh/g, after circulating ten weeks, voltage is appointed and is so the most substantially decayed.
Embodiment 17
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With aphthacene-DME-metallic sodium liquid positive electrode constructed can the system of charge and discharge room temperature liquid metal battery Preparation Method, and charge-discharge performance.
Its concrete preparation method is:
1, take the aphthacene-DME-metallic sodium liquid positive electrode 10mL prepared to be injected into shown in Fig. 2 As positive pole in stainless steel case.
2, by ready Na3Zr2Si2PO12Pipe is made in being inserted into the stainless steel case equipped with liquid positive electrode For electrolyte and barrier film.
3, taking the liquid negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL is injected into State Na3Zr2Si2PO12As negative pole in pipe, ready aluminum net is inserted into negative pole liquid as afflux simultaneously Body.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharge cut-off voltage is 0.6V, charge cutoff Pressure is 1.3V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 19, it can be seen that its specific discharge capacity can Reach 120mAh/g, charge specific capacity 105mAh/g.
Embodiment 18
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With Na2S8-DMSO liquid positive electrode constructed can the preparation method of charge and discharge room temperature liquid metal battery, And charge-discharge performance.
Its concrete preparation method is:
1, the Na prepared is taken2S8-DMSO liquid positive electrode 10mL is injected into the rustless steel shown in Fig. 4 As positive pole in shell.
2, by Na-β "-Al2O3Earthenware is inserted into conduct electricity in the stainless steel case equipped with liquid positive electrode Solve matter and barrier film.
3, taking the liquid metal negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL injects To above-mentioned Na-β "-Al2O3As negative pole in earthenware, ready aluminum net is inserted into negative pole liquid simultaneously As collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharge cut-off voltage is 1.5V, charge cutoff Pressure is 2.1V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 20, it can be seen that its first Zhou Fang electricity specific volume Amount is up to 160mAh/g, charge specific capacity 159mAh/g, and efficiency for charge-discharge is 99%.To biphenyl-DME- Metallic sodium liquid metal negative pole carries out safety experiment, and Figure 21 is golden for biphenyl-DME-after dripping many sulphions Belong to sodium solution to scheme over time, from figure, can be seen that biphenyl-DME-metallic sodium reacts with many sulphions Gentleer, further illustrate the cell safety of biphenyl-DME-metallic sodium solution negative pole and many sulphions composition Performance is higher.
Embodiment 19
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With Na2S12-DMSO liquid positive electrode constructed can the preparation method of charge and discharge room temperature liquid metal battery, And charge-discharge performance.
Its concrete preparation method is:
1, the Na prepared is taken2S12-DMSO liquid positive electrode 10mL is injected into the rustless steel shown in Fig. 4 As positive pole in shell.
2, by Na-β "-Al2O3Earthenware is inserted into conduct electricity in the stainless steel case equipped with liquid positive electrode Solve matter and barrier film.
3, taking the liquid metal negative material prepared, such as biphenyl-DME-metallic sodium solution 10mL injects To above-mentioned Na-β "-Al2O3As negative pole in earthenware, ready aluminum net is inserted into negative pole liquid simultaneously As collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharge cut-off voltage is 1.6V, charge cutoff Pressure is 2.5V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 22, it can be seen that its first Zhou Fang electricity specific volume Amount is up to 250mAh/g, charge specific capacity 250mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 20
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with S-white carbon black slurry positive electrode constructed can the preparation method of charge and discharge room temperature liquid metal battery, And charge-discharge performance.
Its concrete preparation method is:
1, weigh sulfur 6mg, white carbon black 1mg and add a certain amount of NaSO3CF3-DOL-DME solution is mixed into Slurry is injected into the stainless steel case shown in Fig. 4 Nei as positive pole.
2, by ready Na3Zr2Si2PO12Pipe is inserted in the stainless steel case equipped with liquid positive electrode As electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, and ready aluminum net is inserted into this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging cuts Being 2.6V to voltage, charging and discharging currents is 0.2mA.Test result is shown in Figure 23, it can be seen that its head is put in week Capacitance is about 79% up to 700mAh/g, charging capacity 550mAh/g, first all coulombic efficiencies, electric discharge Potential plateau is about 1.7～1.9V.When discharge and recharge scope is 1.7～2.8V, its test result such as figure Shown in 24, its first all discharge capacity is 360mAh/g, and charging capacity is 340mAh/g, coulombic efficiency 94%.
Embodiment 21
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with tetramethoxy piperidines-PC-sodium perchlorate liquid positive electrode constructed can charge and discharge room temperature liquid The preparation method of metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, take the tetramethoxy piperidines-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected into As positive pole in stainless steel case shown in Fig. 4.
2, Na-β "-Al will be got out2O3Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β″-Al2O3As negative pole in earthenware, ready aluminum net is inserted into this negative pole liquid simultaneously and makees For collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid State metal battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 2.5V, and charging cuts Being 3.6V to voltage, charging and discharging currents is 0.04mA.Test result is shown in Figure 25, it can be seen that its head fills in week Capacitance is about 97% up to 205mAh/g, discharge capacity 200mAh/g, first all coulombic efficiencies, fill, Discharge potential platform is about 3.1～3.4V.
Embodiment 22
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative pole material provided by the present invention is described Material, with K3Fe(CN)6What aqueous solution was constructed can the concrete preparation method of charge-discharge battery and discharge and recharge thereof Performance.
Its concrete preparation method is:
1, the K prepared is taken3Fe(CN)6It is stainless that aqueous solution positive electrode 10mL is injected into shown in Fig. 4 As positive pole in box hat.
2, by ready Na3Zr2Si2PO12Earthenware is inserted into the rustless steel equipped with liquid positive electrode As electrolyte and barrier film in shell.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into this negative pole liquid simultaneously and makees For collector.
4, obtained cell mouth is fully sealed i.e. can get energy-storage battery of the present invention
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 2.5V, and charging cuts Being 3.8V to voltage, charging and discharging currents is 0.04mA.Test result is shown in Figure 26, it can be seen that its head fills in week Capacitance is about 91% up to 68mAh/g, discharge capacity 74mAh/g, first all coulombic efficiencies, fills, puts Electric potential platform is about 3.1～3.3V.
Embodiment 23
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With benzophenone-DME-metallic sodium liquid positive electrode constructed can charge and discharge room temperature liquid metal battery Preparation method, and charge-discharge performance.
Its concrete preparation method is:
1, take the benzophenone-DME-metallic sodium solution positive electrode 10mL prepared to be injected into shown in Fig. 4 Stainless steel case in as positive pole.
2, by ready Na-β "-Al2O3Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β″-Al2O3As negative pole in earthenware, ready aluminum net is inserted into simultaneously this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get energy-storage battery of the present invention
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 0.8V, charge by Voltage is 1.5V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 27, it can be seen that its first Zhou Fang electricity holds Measuring up to 300mAh/g, charging capacity 250mAh/g, first all coulombic efficiencies are about 83%, and discharge potential is put down Platform is about 0.8～1V.
Embodiment 24
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With iodo-PC-sodium perchlorate liquid positive electrode constructed can the preparation side of charge and discharge room temperature liquid metal battery Method, and charge-discharge performance.
Its concrete preparation method is:
1, take the iodo-PC-sodium perchlorate solution positive electrode 10mL prepared and be injected into shown in Fig. 4 not As positive pole in rust box hat.
2, by ready Na3Zr2Si2PO12Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into simultaneously this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 2V, and charging is by electricity Pressure is 3V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 28, it can be seen that its first all discharge capacity can Reaching 200mAh/g, charging capacity 210mAh/g, first all coulombic efficiencies are about 95%, and charge and discharge current potential is put down Platform is about 2.8～3.0V.
Embodiment 25
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With ferrocene-PC-sodium perchlorate liquid positive electrode constructed can the system of charge and discharge room temperature liquid metal battery Preparation Method, and charge-discharge performance.
Its concrete preparation method is:
1, take the ferrocene-PC-sodium perchlorate solution positive electrode 10mL prepared to be injected into shown in Fig. 4 Stainless steel case in as positive pole.
2, by ready Na3Zr2Si2PO12Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into simultaneously this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 2.5V, charge by Voltage is 3.1V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 29, it can be seen that its first all charging capacity Up to 200mAh/g, discharge capacity 210mAh/g, first all coulombic efficiencies are about 95%, charge and discharge current potential Platform is about 2.7～3.0V.
Embodiment 26
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With acenaphthene-DME-metallic sodium liquid positive electrode constructed can the preparation side of charge and discharge room temperature liquid metal battery Method, and charge-discharge performance.
Its concrete preparation method is:
1, take the acenaphthene-DME-metallic sodium solution 10mL prepared and be injected into the stainless steel case shown in Fig. 4 Nei work For positive pole.
2, by ready Na-β "-Al2O3Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β″-Al2O3As negative pole in earthenware, ready aluminum net is inserted into simultaneously this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 0V, and charging is by electricity Pressure is 0.65V, and charging and discharging currents is 0.02mA.Test result is shown in Figure 30, it can be seen that its first week charging is held Measuring up to 150mAh/g, charging capacity 130mAh/g, first all coulombic efficiencies are about 86%, and discharge potential is put down Platform is about 0.2～0.3V.
Embodiment 27
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With quinoline woods-PC-sodium perchlorate liquid positive electrode constructed can the system of charge and discharge room temperature liquid metal battery Preparation Method, and charge-discharge performance.
Its concrete preparation method is:
1, take the quinoline woods-PC-sodium perchlorate solution 10mL prepared and be injected into the rustless steel shown in Fig. 4 As positive pole in shell.
2, by ready Na3Zr2Si2PO12Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the biphenyl-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na3Zr2Si2PO12As negative pole in earthenware, ready aluminum net is inserted into simultaneously this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, charge by Voltage is 2.6V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 31, it can be seen that its first Zhou Fang electricity holds Measuring up to 120mAh/g, charging capacity 80mAh/g, first all coulombic efficiencies are about 67%.
Embodiment 28
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described, With anthraquinone-PC-sodium perchlorate liquid positive electrode constructed can the preparation of charge and discharge room temperature liquid metal battery Method, and charge-discharge performance.
Its concrete preparation method is:
1, take the anthraquinone-PC-sodium perchlorate solution 10mL prepared and be injected into the stainless steel case shown in Fig. 4 Interior as positive pole.
2, by ready Na-β "-Al2O3Earthenware is inserted into the stainless steel case equipped with liquid positive electrode Interior as electrolyte and barrier film.
3, take the naphthalene-DME-metallic sodium liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β″-Al2O3As negative pole in earthenware, ready aluminum net is inserted into simultaneously this negative pole liquid as Collector.
4, obtained cell mouth is fully sealed i.e. can get the present invention can charge and discharge room temperature liquid gold Belong to battery.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, charge by Voltage is 2.6V, and charging and discharging currents is 0.2mA.Test result is shown in Figure 32, it can be seen that its first all discharge capacity Up to 215mAh/g, charging capacity 209mAh/g, first all coulombic efficiencies are about 97%, discharge potential 1.6～1.8V.
Embodiment 29
The present embodiment is used for biphenyl-DME-metallic sodium liquid metal negative material provided by the present invention is described The reversibility of electrochemical reaction.
Method particularly includes:
1, anthraquinone 5mg and the poly(ethylene oxide) of excess are mixed homogeneously in the ratio of 5:1 it is simultaneously introduced one It is coated in Na-β "-Al after quantitative PC-sodium perchlorate supporting electrolyte2O3On potsherd.
2, the liquid metal negative pole taking the NaBP containing 4.1mg drops in bottom button cell shell.
3, Na-the β "-Al of anthraquinone it is coated with2O3Potsherd is pressed on liquid metal negative pole, buckles bonnet Test afterwards.
The test of battery uses constant current charge-discharge pattern to carry out, and discharging by voltage is 1.0V, charge by Voltage is 2.7V, and charging and discharging currents is 0.1mA.Test result is shown in that Figure 33 specific capacity is according to NaBP mass meter Obtain, it can be seen that its first all discharge capacity is 76mAh/g, and charging capacity 65mAh/g, this illustrates NaBP The high reversible of storage sodium.
In the various embodiments described above, provide the present invention can the preparation method of charge and discharge room temperature liquid metal battery It is illustrated with performance, although in various embodiments, using biphenyl-DME-metallic sodium as liquid metal Negative material is illustrated, but can not limit protection scope of the present invention with this.The present invention fills The negative material putting room temperature liquid metal battery can include that the liquid metal that the embodiment of the present invention 1 provides is born Any one in the material of pole.
The liquid metal negative material provided in the above embodiment of the present invention has the mobility of liquid, good Electronic conduction and ionic conductivity, low current potential, high safety and good wetting property, will This material has the characteristic of high-energy-density, long circulation life as the battery that negative pole is prepared as, and can be used for The storage of the power station such as solar energy, wind energy output electric energy.
The embodiment of the present invention provide can the structure of charge and discharge room temperature liquid metal battery, can be such as above-mentioned each reality Execute the cylindrical battery as shown in Figure 4 described in example, it is also possible to be double flow battery as shown in Figure 5, Or single flow battery as shown in Figure 6, or flat metal battery as shown in Figure 7.Below, divide Not with embodiment 30-embodiment 33 embodiment of the present invention is provided can charge and discharge room temperature liquid metal battery Structure is described in detail again.
Embodiment 30
The present embodiment in order to the embodiment of the present invention is provided cylindric can charge and discharge room temperature liquid metal battery Structure illustrates.
As shown in Figure 4, Fig. 4 is the structural representation of cylindrical battery.The pictorial diagram of cylindrical battery can With as shown in figure 34.As shown in Figure 4, cylindrical battery may include that Stainless Steel Shell and solid electrolytic Matter pipe；
Described solid electrolyte tube is contactless to be nested in described stainless steel case body, described Stainless Steel Shell Confined space between inwall and described solid electrolyte tube outer wall is used for housing described liquid positive electrode； It is used in described solid electrolyte tube housing described liquid metal negative material.
During electric discharge, electronics arrives positive pole by external circuit from negative pole and is reduced by positive active material, sodium simultaneously Ion arrives positive pole by solid electrolyte from negative pole.Charging process is then, and electronics arrives negative pole from positive pole, Ion also arrives negative pole from positive pole by solid electrolyte simultaneously.
Embodiment 31
The present embodiment can charge and discharge room temperature liquid metal battery in order to the Dual-flow that provides the embodiment of the present invention Structure illustrates.
As it is shown in figure 5, battery container, solid electrolyte film, positive pole fluid reservoir, negative pole fluid reservoir and two Individual pump；
Described battery container is divided into airtight positive pole space and negative pole space by described solid electrolyte film, Wherein said positive pole space is connected with described positive pole fluid reservoir, by a pump by accommodating in positive pole fluid reservoir Described liquid positive electrode pump in described positive pole space, described negative pole space and described negative pole fluid reservoir It is connected, described liquid metal negative material accommodating in negative pole fluid reservoir is pumped into described negative by a pump In space, pole.Operation principle to cylindric can charge and discharge room temperature liquid metal battery similar, repeat no more.
Embodiment 32
The present embodiment can charge and discharge room temperature liquid metal battery in order to single liquid stream of providing the embodiment of the present invention Structure illustrates.
As shown in Figure 6, battery container, solid electrolyte film, positive pole fluid reservoir and pump；
Described battery container is divided into airtight positive pole space and negative pole space by described solid electrolyte film, Wherein said positive pole space is connected with described positive pole fluid reservoir, by described pump by accommodating in positive pole fluid reservoir Described liquid positive electrode pump in described positive pole space, described negative pole space is used for housing described liquid Metal negative electrode material.Operation principle to cylindric can charge and discharge room temperature liquid metal battery similar, repeat no more.
Embodiment 33
The present embodiment can the knot of charge and discharge room temperature liquid metal battery in order to the flat board that provides the embodiment of the present invention Structure illustrates.
As it is shown in fig. 7, battery container and solid electrolyte film；
Described battery container is divided into airtight positive pole space and negative pole space by described solid electrolyte film, Described positive pole space is used for housing described liquid positive electrode, and described negative pole space is used for housing described liquid Metal negative electrode material.Operation principle to cylindric can charge and discharge room temperature liquid metal battery similar, repeat no more.
Above-described detailed description of the invention, is carried out the purpose of the present invention, technical scheme and beneficial effect Further describe, be it should be understood that the foregoing is only the present invention detailed description of the invention and , the protection domain being not intended to limit the present invention, all within the spirit and principles in the present invention, done Any modification, equivalent substitution and improvement etc., should be included within the scope of the present invention.

Claims (17)

1. a liquid metal negative material, it is characterised in that described negative material is alkali metal, fragrance The blackish green liquid that compounds of group and ether solvent mixing generate；
Wherein, any one or more during described alkali metal is metallic sodium, lithium metal or metallic potassium；
Described aromatic compound is biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene Derivant in any one or more；
Described ether solvent include ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, four Glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl-butyl ether, butyl oxide, diamyl ether, two different Amyl ether, two hexyl ethers, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, 4-methyl isophthalic acid, 3- Dioxolanes, dimethoxymethane, 1,2-dimethoxy propane, dioxolane, Isosorbide-5-Nitrae-dioxy six Ring, oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide, sulfolane or two Any one or more in methyl sulfone.
2. a preparation method for the liquid metal negative material as described in the claims 1, its Being characterised by, described method includes:
In the protective atmosphere of argon, alkali metal and aromatic compound are added according to certain mol proportion In ether solvent, stand, obtain described liquid metal negative material；
Wherein, any one or more during described alkali metal is metallic sodium, lithium metal or metallic potassium；
Described aromatic compound is biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene Derivant in any one or more；
Described ether solvent include ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, four Glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl-butyl ether, butyl oxide, diamyl ether, two different Amyl ether, two hexyl ethers, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, 4-methyl isophthalic acid, 3- Dioxolanes, dimethoxymethane, 1,2-dimethoxy propane, dioxolane, Isosorbide-5-Nitrae-dioxy six Ring, oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide, sulfolane or two Any one or more in methyl sulfone.
3. the liquid metal negative material that a kind comprises described in the claims 1 can charge and discharge room temperature Liquid metal cell.
The most according to claim 3 can charge and discharge room temperature liquid metal battery, it is characterised in that Described can also include by charge and discharge room temperature liquid metal battery:
One in liquid positive electrode or slurry positive electrode, and ionic conduction, electronic isolation Solid electrolyte film；
Wherein, described solid electrolyte film includes for conducts sodium ions, lithium ion or potassium ion Na3Zr2Si2PO12Pottery, Na-β "-Al2O3Pottery, K-β "-Al2O3Pottery, Li7La3Zr2O12Pottery or Li10GeP2S12Any one in pottery.
The most according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterised in that The preparation method of described slurry positive electrode includes:
The pressed powder of positive active material, carbon dust are pressed certain mass than mix homogeneously, add certain Amount supporting electrolyte and be stirred, i.e. obtain described slurry positive electrode；
Wherein, described positive active material includes: Na0.44MnO2、NaTi2(PO4)3、Na3V2(PO4)3、 Na0.8Li0.1Ni0.25Mn0.65O2、NaMg0.1Ni0.4Mn0.2Ti0.3O2, S, K3Fe(CN)6、Na4Fe(CN)6、FePO4 In any one or more.
The most according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterised in that The preparation method of described slurry positive electrode includes:
Liquid positive electrode, carbon dust are pressed certain mass than mix homogeneously, add and a certain amount of support electricity Solve matter and be stirred, i.e. obtaining described slurry positive electrode.
7. according to described in claim 4 or 6 can charge and discharge room temperature liquid metal battery, its feature exists In, described liquid positive electrode is:
With 1,4-benzoquinone, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, the spreading out of acenaphthenequinone In the derivant of biological, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, with glycol dimethyl ether, Allyl carbonate or tetraethyleneglycol dimethyl ether, dimethylformamide or N-Methyl pyrrolidone any one or The multiple solvent that is mixed into, the liquid of composition.
8. according to claim 4 or 6 arbitrary described can charge and discharge room temperature liquid metal battery, it is special Levying and be, the preparation method of described liquid positive electrode includes:
1,4-benzoquinone with 0.1～5mol, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthene In the derivant of quinone, the derivant of acenaphthenequinone, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, molten Solution in 1L with glycol dimethyl ether, Allyl carbonate, tetraethyleneglycol dimethyl ether, dimethyl formyl In the solvent of amine or any one or more mixing of N-Methyl pyrrolidone, add a certain amount of support and be electrolysed Matter, i.e. obtains described liquid positive electrode.
9. according to described in claim 4 or 6 can charge and discharge room temperature liquid metal battery, its feature exists In, described liquid positive electrode is:
In benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene arbitrary as solute, with glycol dinitrate Ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethylformamide or N-Methyl pyrrolidone Any one or more is mixed into solvent, the liquid of composition.
10. according to claim 4 or 6 arbitrary described can charge and discharge room temperature liquid metal battery, it is special Levying and be, the preparation method of described liquid positive electrode includes:
In benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene with 0.1～5mol any one or more It is mixed into solute, is dissolved in the glycol dimethyl ether of 1L, diethylene glycol dimethyl ether, TEG diformazan In the solvent of any one or more mixing of ether, dimethylformamide or N-Methyl pyrrolidone, add one Quantitative alkali metal, stands, i.e. obtains described liquid positive electrode.
11. according to described in claim 4 or 6 can charge and discharge room temperature liquid metal battery, its feature exists In, described liquid positive electrode is:
With Na2SxFor solute, with dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, Dimethylformamide, N-Methyl pyrrolidone or water any one or more be mixed into solvent constitute solution； Wherein, 3≤x≤12.
12. according to described in claim 4 or 6 can charge and discharge room temperature liquid metal battery, its feature exists In, the preparation method of described liquid positive electrode includes:
According to Na2The mol ratio of S/S=1/ (x-1) is by Na2S Yu S adds dimethyl sulfoxide, diethylene glycol Dimethyl ether, tetraethyleneglycol dimethyl ether, dimethylformamide, N-Methyl pyrrolidone or water any one or many Kind mixing solvent in, and add a certain amount of supporting electrolyte stir to being completely dissolved, i.e. obtain institute State liquid positive electrode；
Wherein, 3≤x≤12.
13. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterised in that Described can charge and discharge room temperature liquid metal battery be cylindrical battery, including:
Stainless Steel Shell and solid electrolyte tube；
Described solid electrolyte tube is contactless to be nested in described stainless steel case body, described stainless steel case Confined space between internal wall and described solid electrolyte tube outer wall is used for housing described liquid positive pole material Material；It is used in described solid electrolyte tube housing described liquid metal negative material.
14. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterised in that Described can charge and discharge room temperature liquid metal battery be double flow battery, including:
Battery container, solid electrolyte film, positive pole fluid reservoir, negative pole fluid reservoir and two pumps；
Described battery container is divided into airtight positive pole space by described solid electrolyte film and negative pole is empty Between, wherein said positive pole space is connected with described positive pole fluid reservoir, by a pump by positive pole fluid reservoir In accommodating described liquid positive electrode pump in described positive pole space, described negative pole space is negative with described Pole fluid reservoir is connected, by a pump by described liquid metal negative material accommodating in negative pole fluid reservoir Pump in described negative pole space.
15. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterised in that Described can charge and discharge room temperature liquid metal battery be single flow battery, including:
Battery container, solid electrolyte film, positive pole fluid reservoir and pump；
Described battery container is divided into airtight positive pole space by described solid electrolyte film and negative pole is empty Between, wherein said positive pole space is connected with described positive pole fluid reservoir, by described pump by positive pole fluid reservoir In accommodating described liquid positive electrode pump in described positive pole space, described negative pole space is used for housing Described liquid metal negative material.
16. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterised in that Described can charge and discharge room temperature liquid metal battery be flat metal battery, including:
Battery container and solid electrolyte film；
Described battery container is divided into airtight positive pole space by described solid electrolyte film and negative pole is empty Between, described positive pole space is used for housing described liquid positive electrode, and described negative pole space is used for housing institute State liquid metal negative material.
As described in 17. 1 kinds of claims as arbitrary in the claims 3-16 can charge and discharge room temperature liquid metal electricity The purposes in pond, it is characterised in that described can charge and discharge room temperature liquid metal battery for solar electrical energy generation, Wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or the extensive energy storage of communication base station Equipment.
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