CN105098140A - Liquid metal anode material, room-temperature liquid metal battery, and preparation method and application - Google Patents
Liquid metal anode material, room-temperature liquid metal battery, and preparation method and application Download PDFInfo
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- CN105098140A CN105098140A CN201410383865.0A CN201410383865A CN105098140A CN 105098140 A CN105098140 A CN 105098140A CN 201410383865 A CN201410383865 A CN 201410383865A CN 105098140 A CN105098140 A CN 105098140A
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a liquid metal anode material, a room-temperature liquid metal battery, and a preparation method and an application. The anode material is a black green liquid which is formed by mixing alkali metal, an aromatic compound and an ether solvent, wherein the alkali metal is any one of metal sodium, metal lithium or metal potassium; and the aromatic compound is any one of biphenyl, derivatives of the biphenyl, naphthaline, derivatives of the naphthaline and anthracene or derivatives of the anthracene; and the ether solvent comprises one or more of glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethylene glycol dimethylether and the like.
Description
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 the regenerative resource such as solar energy, wind energy extremely urgent.But, due to fluctuation and the intermittent instability that result in electrical network of solar energy, wind energy, so need to greatly develop extensive energy storage technology.Extensive energy storage technology effectively can solve the problem of the regenerative resource such as solar energy, wind energy intermittence power supply, realizes demand management, eliminates peak-valley difference, level and smooth load etc. round the clock.
Extensive energy storage technology main at present has pumped storage, compressed-air energy storage, flywheel energy storage, electrochemical energy storage etc.Various energy storage technology has respective service condition and advantage, is all in positive research and development and demonstration stage.Wherein energy storage chemical power source such as sodium-sulphur battery, all-vanadium flow battery, lithium ion battery has had some to demonstrate as extensive energy storage device.
But sodium-sulphur battery needs to run under 300 degree of high temperature, the direct use of molten metal sodium and sulphur result in this battery and there is serious etching problem and potential safety hazard.All-vanadium flow battery vanadium ion used belongs to extremely toxic substance and resource-constrained, there is the problem of the phase counterdiffusion of both positive and negative polarity active material in addition, and the energy density of this energy-storage battery is not high in its running.Lithium ion battery has good performance as extensive energy-storage battery, but the manufacturing cost of lithium-ion energy storage battery is high.Therefore at present not a kind of energy-storage battery can meet the comprehensive requirements such as low cost, fail safe are good, abundant raw materials.
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 has the mobility of liquid, good electron conduction and ionic conductivity, low current potential, high fail safe and good wetting property, this material is had the characteristic of high-energy-density, long circulation life as the battery that negative pole is prepared into, can be used for the storage that the power station such as solar energy, wind energy exports electric energy.
First aspect, embodiments providing a kind of negative material is the blackish green liquid that the mixing of alkali metal, aromatic compound and ether solvent generates;
Wherein, described alkali metal be in sodium metal, lithium metal or metallic potassium any one or multiple;
Described aromatic compound be biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene derivative in any one or multiple;
Described ether solvent comprises ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol 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-dioxolanes, dimethoxymethane, 1,2-dimethoxy propane, dioxolane, 1, in 4-dioxane, oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide (DMSO), sulfolane or dimethyl sulfone any one or multiple.
Second aspect, embodiments provide a kind of preparation method of the liquid metal negative material as described in above-mentioned first aspect, described method comprises:
In the protective atmosphere of argon gas, alkali metal and aromatic compound are added in ether solvent according to certain mol proportion, leave standstill, obtain described liquid metal negative material;
Wherein, described alkali metal be in sodium metal, lithium metal or metallic potassium any one or multiple;
Described aromatic compound be biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene derivative in any one or multiple;
Described ether solvent comprises ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol 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-dioxolanes, dimethoxymethane, 1,2-dimethoxy propane, dioxolane, 1, in 4-dioxane, oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide (DMSO), sulfolane or dimethyl sulfone any one or multiple.
The third aspect, embodiments provide a kind of comprise liquid metal negative material described in above-mentioned first aspect can charge and discharge room temperature liquid metal battery.
Preferably, describedly can also to comprise 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 comprises the Na for conducts sodium ions, lithium ion or potassium ion
3zr
2si
2pO
12pottery, Na-β "-Al
2o
3pottery, K-β "-Al
2o
3pottery, Li
7la
3zr
2o
12pottery or Li
10geP
2s
12any one in pottery.
Preferably, the preparation method of described slurry positive electrode comprises:
The pressed powder of positive active material, carbon dust are mixed by certain mass ratio, adds a certain amount of supporting electrolyte and stir, namely obtain described liquid positive electrode;
Wherein, described positive active material comprises: Na
0.44mnO
2, NaTi
2(PO
4)
3, Na
3v
2(PO
4) 3, Na
0.8li
0.1ni
0.25mn
0.65o
2, NaMg
0.1ni
0.4mn
0.2ti
0.3o
2, S, K
3fe (CN)
6, Na
4fe (CN)
6, FePO
4in any one or more.
Preferably, the preparation method of described slurry positive electrode comprises:
Liquid positive electrode, carbon dust are mixed by certain mass ratio, adds a certain amount of supporting electrolyte and stir, namely obtain described liquid positive electrode.
Preferred further, described liquid positive electrode is:
So that in the derivative of the derivative of the derivative of the derivative of 1,4-benzoquinone, 1,4-benzoquinone, anthraquinone, anthraquinone, acenaphthenequinone, acenaphthenequinone, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, with glycol dimethyl ether, propene carbonate, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE, any one or more is mixed into solvent, the liquid of formation.
Preferred further, the preparation method of described liquid positive electrode comprises:
So that in the derivative of the derivative of the derivative of the derivative of the 1,4-benzoquinone of 0.1 ~ 5mol, 1,4-benzoquinone, anthraquinone, anthraquinone, acenaphthenequinone, acenaphthenequinone, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, be dissolved in 1L with glycol dimethyl ether, propene carbonate, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE any one or more mixing solvent in, add a certain amount of supporting electrolyte, namely obtain described liquid positive electrode.
Preferred further, described liquid positive electrode is:
With arbitrary for solute in benzophenone, acenaphthene, aphthacene, pentacene or pyrene, with glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE, any one or more is mixed into solvent, the liquid of formation.
Preferred further, the preparation method of described liquid positive electrode comprises:
So that in the benzophenone of 0.1 ~ 5mol, acenaphthene, aphthacene, pentacene or pyrene, any one or more is mixed into solute, be dissolved in any one or more mixed solvent of the glycol dimethyl ether of 1L, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE, add a certain amount of alkali metal, leave standstill, namely obtain described liquid positive electrode.
Preferred further, described liquid positive electrode is:
With Na
2s
xfor solute, with dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide, 1-METHYLPYRROLIDONE or water, any one or more is mixed into the solution that solvent is formed; Wherein, 3≤x≤12.
Preferred further, the preparation method of described liquid positive electrode comprises:
According to Na
2the mol ratio of S/S=1/ (x-1) is by Na
2s and S adds in the arbitrary solvent of dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or dimethyl formamide or 1-METHYLPYRROLIDONE or water, and adds a certain amount of supporting electrolyte and be stirred to and dissolve completely, namely obtains described liquid positive electrode;
Wherein, 3≤x≤12.
Preferred further, described can charge and discharge room temperature liquid metal battery be cylindrical battery, comprising:
Stainless Steel Shell and solid electrolyte tube;
Described solid electrolyte tube is contactless to be nested in described Stainless Steel Shell, and the confined space between described Stainless Steel Shell inwall and described solid electrolyte tube outer wall is used for accommodating described liquid positive electrode; For accommodating described liquid metal negative material in described solid electrolyte tube.
Preferred further, described can charge and discharge room temperature liquid metal battery be double flow battery, comprising:
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, described liquid positive electrode accommodating in positive pole fluid reservoir is pumped in described positive pole space, described negative pole space is connected with described negative pole fluid reservoir, is pumped in described negative pole space by described liquid metal negative material accommodating in negative pole fluid reservoir by a pump.
Preferred further, described can charge and discharge room temperature liquid metal battery be single flow battery, comprising:
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, pump in described positive pole space by described pump by described liquid positive electrode accommodating in positive pole fluid reservoir, described negative pole space is used for accommodating described liquid metal negative material.
Preferred further, described can charge and discharge room temperature liquid metal battery be flat metal battery, comprising:
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, and described positive pole space is used for accommodating described liquid positive electrode, and described negative pole space is used for accommodating described liquid metal negative material.
Fourth aspect, embodiments provide a kind of as described in the above-mentioned third aspect can the purposes of charge and discharge room temperature liquid metal battery, describedly can be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station by charge and discharge room temperature liquid metal battery.
The liquid metal negative material that the embodiment of the present invention provides has the mobility of liquid, good electron conduction and ionic conductivity, low current potential, high fail safe and good wetting property, with low cost, rich material resources, this material is had the characteristic of high-energy-density, long circulation life as the battery that negative pole is prepared into, can be used for the storage that the power station such as solar energy, wind energy exports 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 electrochemical impedance spectrogram of the biphenyl-DME-sodium metal liquid metal negative pole that Fig. 1 provides for the embodiment of the present invention 2;
Biphenyl-DME-sodium metal the solution that Fig. 2 provides for the embodiment of the present invention 2 drips the solution variation diagram in time after deionized water;
The solubility schematic diagram of the liquid negative pole of biphenyl-DME-sodium metal that Fig. 3 provides for the embodiment of the present invention 2;
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;
Ten weeks charge-discharge performance curves before the liquid negative material that Fig. 8 provides for the embodiment of the present invention 9 and the battery that anthraquinone liquid positive electrode constructs;
The liquid metal negative material that Fig. 9 provides for the embodiment of the present invention 9 and the cycle performance of battery curve that anthraquinone liquid positive electrode constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 10 provides for the embodiment of the present invention 10 and the battery that anthraquinone-carbon black slurry positive pole constructs;
The liquid metal negative material that Figure 11 provides for the embodiment of the present invention 11 and battery first three week charge-discharge performance curve that benzoquinones liquid positive electrode constructs;
The liquid metal negative material that Figure 12 provides for the embodiment of the present invention 12 and the battery charging and discharging performance curve that acenaphthenequinone liquid positive electrode constructs;
Anthraquinone-PC-the sodium perchlorate that Figure 13 provides for the embodiment of the present invention 12, benzoquinones-PC-sodium perchlorate, acenaphthenequinone-PC-sodium perchlorate are the head week discharge and recharge comparison diagram of liquid positive electrode;
The liquid metal negative material that Figure 14 provides for the embodiment of the present invention 13 and NaTi
2(PO
4)
3the charge-discharge performance curve of the battery constructed;
The liquid metal negative material that Figure 15 provides for the embodiment of the present invention 13 and NaTi
2(PO
4)
3the cycle performance curve of the battery constructed;
The liquid metal negative material that Figure 16 provides for the embodiment of the present invention 14 and Na
3v
2(PO
4)
3the charge-discharge performance curve of the battery constructed;
The liquid metal negative material that Figure 17 provides for the embodiment of the present invention 15 and Na
0.44mnO
2the charge-discharge performance curve of the battery of structure;
The liquid metal negative material that Figure 18 provides for the embodiment of the present invention 16 and the battery charging and discharging performance curve that pyrene-DME liquid positive pole forms;
The liquid metal negative material that Figure 19 provides for the embodiment of the present invention 17 and the battery charging and discharging performance curve that aphthacene-DME liquid positive pole forms;
The liquid metal negative material that Figure 20 provides for the embodiment of the present invention 18 and Na
2s
8the battery charging and discharging performance curve of liquid positive pole composition;
After the many sulphions of dropping that Figure 21 provides for the embodiment of the present invention 18, biphenyl-DME-sodium metal solution is schemed over time;
The liquid metal negative material that Figure 22 provides for the embodiment of the present invention 19 and Na
2s
12the battery charging and discharging performance curve of liquid positive pole composition;
The liquid metal negative material that Figure 23 provides for the embodiment of the present invention 20 and the charge-discharge performance curve of battery between 1.5 ~ 2.7V that S-carbon black slurry positive pole constructs;
The liquid metal negative material that Figure 24 provides for the embodiment of the present invention 20 and the charge-discharge performance curve of battery between 1.7 ~ 2.8V that S-carbon black slurry positive pole constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 25 provides for the embodiment of the present invention 21 and the battery that tetramethoxy piperidines liquid positive pole constructs;
The liquid metal negative material that Figure 26 provides for the embodiment of the present invention 22 and K
3fe (CN)
6the charge-discharge performance curve of the battery that the aqueous solution constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 27 provides for the embodiment of the present invention 23 and the battery that benzophenone constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 28 provides for the embodiment of the present invention 24 and the battery that iodine liquid positive pole constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 29 provides for the embodiment of the present invention 25 and the battery that ferrocene liquid positive pole constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 30 provides for the embodiment of the present invention 26 and the battery that acenaphthene liquid positive pole constructs;
The charge-discharge performance curve of the liquid metal negative material that Figure 31 provides for the embodiment of the present invention 27 and the battery that quinoline woods liquid positive pole constructs;
The battery charging and discharging performance curve that the liquid negative pole of the naphthalene-DME-sodium metal that Figure 32 provides for the embodiment of the present invention 28 and anthraquinone-PC-sodium perchlorate liquid positive pole form;
The battery charging and discharging curve of the biphenyl-DME-sodium metal that Figure 33 provides for the embodiment of the present invention 29 and excessive anthraquinone solution composition;
The pictorial diagram of the cylindrical battery that Figure 34 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended to limit the scope of the invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of liquid metal negative material.
Wherein, described negative material is the blackish green liquid that the mixing of alkali metal, aromatic compound and ether solvent generates;
Concrete, described alkali metal can be any one or multiple mixing in sodium metal (Na), lithium metal (Li) or metallic potassium (K);
Described aromatic compound can be any one or multiple mixing in the derivative of biphenyl (BP), connection benzene derivate, naphthalene (NP), naphthalene derivatives, anthracene or anthracene;
Wherein, Connection benzene derivate is specifically as follows: biphenyl, DCBP, tetrachloro biphenyl terphenyl, x-methyl biphenyl, x-ethyl biphenyl etc.;
Naphthalene derivatives is specifically as follows: phenanthrene, dichloronaphtalene, Tetrachloronaphthalene, x-methyl naphthalene, Isosorbide-5-Nitrae-dimethylnaphthalene, x-ethylnaphthalene.
Described ether solvent comprises 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-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, dimethoxymethane, 1, 2-dimethoxy propane, dioxolane, 1, 4-dioxane, oxirane, expoxy propane, 1, 1-diethoxyethane, dimethyl sulfoxide (DMSO), any one or multiple mixing in sulfolane or dimethyl sulfone.Wherein be preferably, the one in DME, DEGDME or TEGDME.
Alkali metal, aromatic compound react after mixing in ether solvent, are described below for sodium, biphenyl and DME solvent.
Course of reaction is as shown in following formula 1:
The characteristic of the liquid metal negative material that distinct fragrance compounds of group and sodium metal generate in DME solvent is given in following table 1.
Table 1
The liquid metal negative material that the embodiment of the present invention provides has the mobility of liquid, good electron conduction and ionic conductivity, low current potential, high fail safe and good wetting property, with low cost, rich material resources, has the characteristic of high-energy-density, long circulation life as battery cathode using this material.
Embodiment 2
The embodiment of the present invention 2 provides a kind of preparation method of the liquid metal negative material as described in above-described embodiment 1.Described method comprises: in the protective atmosphere of argon gas, adds in ether solvent by alkali metal and aromatic compound according to certain mol proportion, leaves standstill, obtains described liquid metal negative material.
Concrete, described alkali metal can be any one or multiple mixing in sodium metal (Na), lithium metal (Li) or metallic potassium (K);
Described aromatic compound can be any one or multiple mixing in the derivative of biphenyl (BP), connection benzene derivate, naphthalene (NP), naphthalene derivatives, anthracene or anthracene;
Wherein, Connection benzene derivate is specifically as follows: biphenyl, DCBP, tetrachloro biphenyl terphenyl, x-methyl biphenyl, x-ethyl biphenyl etc.;
Naphthalene derivatives is specifically as follows: phenanthrene, dichloronaphtalene, Tetrachloronaphthalene, x-methyl naphthalene, Isosorbide-5-Nitrae-dimethylnaphthalene, x-ethylnaphthalene.
Described ether solvent comprises 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-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, dimethoxymethane, 1, 2-dimethoxy propane, dioxolane, 1, 4-dioxane, oxirane, expoxy propane, 1, 1-diethoxyethane, dimethyl sulfoxide (DMSO), any one or multiple mixing in sulfolane or dimethyl sulfone.Wherein be preferably, the one in DME, DEGDME or TEGDME.
Below, be specifically described for the preparation process of biphenyl-DME-sodium metal liquid metal negative pole.
It is stand-by that in the glove box being full of Ar gas, the ratio of 1:1 takes sodium metal 0.23g in molar ratio, biphenyl 1.54g puts into same 20ml measuring cup.Getting 10mL glycol dimethyl ether (DME) liquid with 10ml liquid-transfering gun is afterwards injected in the measuring cup being placed with sodium metal, biphenyl, and now solution becomes rapidly blackish green.The blackish green solution left standstill obtained can be obtained the liquid metal negative pole of biphenyl-DME-sodium metal for 2 hours.Fig. 1 is the electrochemical impedance spectrogram of above-mentioned biphenyl-DME-sodium metal liquid metal negative pole, can find out that resistance is 86 ohm when concentration is 1mol/l from figure.σ can be calculated by Conductivity formula σ=k/R
1mol/l=1.2x10
-2s/cm, our test simultaneously obtains the conductivityσ of 1mol/l biphenyl-DME-lithium metal
1mol/l=1.1x10
-2s/cm.Above-mentioned biphenyl-DME-sodium metal liquid metal negative pole safety experiment is illustrated by Fig. 2, and-the DME-of biphenyl shown in figure sodium metal solution drips the solution variation diagram in time after deionized water.Can find out that from figure the reaction of biphenyl-DME-sodium metal solution and water is inviolent as metal sodium and water reaction, illustrate that biphenyl-DME-sodium metal solution is used as the security performance of negative pole higher than sodium metal negative pole.The solubility experiment of the liquid negative pole of above-mentioned biphenyl-DME-sodium metal is illustrated by Fig. 3, can find out that the solubility of biphenyl-DME-sodium metal is greater than 5mol/l from figure, calculate according to the specific capacity 151mAh/g of biphenyl-DME-sodium metal, the volume and capacity ratio obtaining biphenyl-DME-sodium metal is 1.4x10
2ah/L, high solubility can obtain high volume energy density.It should be noted that, concentration of the present invention all calculates by biphenyl concentration, and wherein biphenyl and alkali-metal molar ratio are 1:1, but this ratio is only used in an embodiment the present invention being described, and proportion of the present invention is not limited thereto ratio.
Embodiment 3
What the embodiment of the present invention additionally provided a kind of liquid metal negative material can charge and discharge room temperature liquid metal 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.
In addition, what the present embodiment provided can also comprise 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 comprises the Na for conducts sodium ions, lithium ion or potassium ion
3zr
2si
2pO
12pottery, Na-β "-Al
2o
3pottery, K-β "-Al
2o
3pottery, Li
7la
3zr
2o
12pottery or Li
10geP
2s
12any one in pottery.
Respectively liquid positive electrode or slurry positive electrode will be described respectively with embodiment 4-8 respectively below.
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 preparation method thereof.
Described liquid positive electrode is:
With arbitrary for solute in the derivative of the derivative of the derivative of the derivative of 1,4-benzoquinone, 1,4-benzoquinone, anthraquinone, anthraquinone, acenaphthenequinone, acenaphthenequinone, phenanthrenequione or phenanthrenequione, arbitrary for solvent with glycol dimethyl ether, propene carbonate or tetraethyleneglycol dimethyl ether, the liquid of formation.
Its preparation method can be:
With arbitrary for solute in the derivative of the derivative of the derivative of the derivative of the 1,4-benzoquinone of 0.1 ~ 5mol, 1,4-benzoquinone, anthraquinone, anthraquinone, acenaphthenequinone, acenaphthenequinone, phenanthrenequione or phenanthrenequione, be dissolved in 1L with in the arbitrary solvent of glycol dimethyl ether, propene carbonate or tetraethyleneglycol dimethyl ether, add a certain amount of supporting electrolyte, namely obtain described liquid positive electrode.
Such as in a concrete example, for anthraquinone-PC-sodium perchlorate liquid positive electrode, its concrete preparation process is:
Take the PC solvent that anthraquinone 2.08g is dissolved in 10mL, add 1.4g trifluoromethyl sulfonate as supporting electrolyte simultaneously, be stirred to dissolving completely and can obtain required liquid positive electrode.
Embodiment 5
The embodiment of the present invention 5 is in order to illustrate a kind of liquid positive electrode described in above-described embodiment 3, and another kind of preparation method.
Described liquid positive electrode is:
With arbitrary for solute in benzophenone, acenaphthene, aphthacene, pentacene or pyrene, arbitrary for solvent with glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether, the liquid of formation.
Its preparation method can be:
With arbitrary for solute in the benzophenone of 0.1 ~ 5mol, acenaphthene, aphthacene, pentacene or pyrene, be dissolved in the arbitrary solvent of the glycol dimethyl ether of 1L, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether, add a certain amount of alkali metal, leave standstill, namely obtain described liquid positive electrode.
Such as in a concrete example, for aphthacene-DME-sodium metal liquid positive electrode, its concrete preparation process is:
Take the DME solvent that aphthacene 2.20g is dissolved in 10mL, the sodium metal simultaneously adding 160mg, as additive, is stirred to dissolving completely and can obtains required liquid positive electrode.
Embodiment 6
The embodiment of the present invention 6 is in order to illustrate a kind of liquid positive electrode described in above-described embodiment 3, and another preparation method.
Described liquid positive electrode is:
With Na
2s
xfor solute, with the arbitrary solution formed for solvent of dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or water; Wherein, 3≤x≤12.
Its preparation method comprises:
According to Na
2the mol ratio of S/S=1/ (x-1) is by Na
2s and S adds in the arbitrary solvent of dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or water, and adds a certain amount of supporting electrolyte and be stirred to and dissolve completely, namely obtains described liquid positive electrode; Wherein, 3≤x≤12.
Such as in a concrete example, with Na
2s
x-DMSO liquid positive electrode is example, and its concrete preparation process is:
According to Na
2the mol ratio of S/S=1/ (x-1) takes appropriate Na
2s and S joins in dimethyl sulfoxide (DMSO) (DMSO) solution, add simultaneously a certain amount of trifluoromethyl sulfonate as supporting electrolyte be stirred to completely dissolve can obtain required liquid positive electrode.This liquid positive electrode has good solubility, the Na such as prepared in this approach
2s
8with Na
2s
4solubility be all greater than 1mol/L.
Embodiment 7
The embodiment of the present invention 7 is in order to illustrate a kind of preparation method of the slurry positive electrode described in above-described embodiment 3.
By Na
0.44mnO
2, NaTi
2(PO
4)
3, Na
3v
2(PO
4)
3, Na
0.8li
0.1ni
0.25mn
0.65o
2, NaMg
0.1ni
0.4mn
0.2ti
0.3o
2, S, K
3fe (CN)
6, Na
4fe (CN)
6, FePO
4deng in the pressed powder of any one or more positive active material, carbon dust mix by certain mass ratio, add a certain amount of supporting electrolyte and stir, namely obtaining described liquid positive electrode.
Embodiment 8
The embodiment of the present invention 8 is in order to illustrate the another kind of preparation method of the slurry positive electrode described in above-described embodiment 3.
Any one the liquid positive electrode provide above-described embodiment 4 or embodiment 5 or embodiment 6 and carbon dust mix by certain mass ratio, add a certain amount of supporting electrolyte and stir, namely obtaining described liquid positive electrode.
Below by some specific embodiments, can the preparation method of charge and discharge room temperature liquid metal battery and performance be described in further detail provided by the invention.
Embodiment 9
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with anthraquinone-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the anthraquinone-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid metal negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charge cutoff 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 reach 300mAh/g, charging capacity 250mAh/g, and first all coulombic efficiencies are about 84%, and discharge potential platform is about 1.75V.Its cycle performance test result as shown in Figure 9, test result show to have circulated 400 weeks after discharge capacity keep 88%.
Embodiment 10
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with anthraquinone-carbon black slurry positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, take anthraquinone 10mg and carbon black 2mg to add and to be injected into after a certain amount of PC-sodium perchlorate solution is mixed into slurry in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that slurry positive electrode is housed.
3, get the liquid negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.2V, and charge cutoff 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 reach 320mAh/g, charging capacity 260mAh/g, and first all coulombic efficiencies are about 81%.
Embodiment 11
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with benzoquinones-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the benzoquinones-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charge cutoff voltage is 2.6V, and charging and discharging currents is 0.4mA.Test result is shown in Figure 11, and can find out that its first all discharge capacity can reach 260mAh/g, charging capacity 300mAh/g, first all coulombic efficiencies are about 86%, and charge and discharge potential plateau is about 2.4V.
Embodiment 12
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with acenaphthenequinone-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the acenaphthenequinone-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charge cutoff voltage is 3V, and charging and discharging currents is 0.4mA.Test result is shown in Figure 12, and can find out that its first all discharge capacity can reach 180mAh/g, charging capacity 160mAh/g, first all coulombic efficiencies are about 88%, and charge and discharge potential plateau is about 1.9 ~ 2.1V.Figure 13 is based on said method, anthraquinone-PC-sodium perchlorate, benzoquinones-PC-sodium perchlorate, acenaphthenequinone-PC-sodium perchlorate is adopted to be the head week discharge and recharge comparison diagram of liquid positive electrode respectively, can find out that from figure employing benzoquinones-PC-sodium perchlorate has the current potential of higher current potential and anthraquinone-PC-sodium perchlorate lower, but can find out that the cyclical stability of anthraquinone-PC-sodium perchlorate best has better prospect from above test.
Embodiment 13
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with NaTi
2(PO
4)
3what constructed can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, by NaTi
2(PO
4)
3powder mixes according to the weight ratio of 80:10:10 with acetylene black, binding agent Kynoar (PVDF), add appropriate 1-METHYLPYRROLIDONE (NMP) solvent, in the environment of air drying, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, is cut into the pole piece coiling of 60 × 20mm after drying at Na-β "-Al
2o
3on earthenware outer wall, insert in stainless steel shell shown in shown in Fig. 4 afterwards, and drip the sodium perchlorate of 400mL, propene carbonate electrolyte as positive pole.
2, get the biphenyl, DME, the sodium metal liquid negative material 10mL that prepare and be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
3, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging by voltage is 2.6V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 14, and can find out that its first all discharge capacity can reach 110mAh/g, charging capacity 109mAh/g, first all coulombic efficiencies are about 99%, and charge and discharge potential plateau is about 1.9 ~ 2.1V.Its cycle performance test result is as Figure 15, and its capacity after 60 weeks that circulates keeps 87%.
Embodiment 14
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with Na
3v
2(PO
4)
3what constructed can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, by Na
3v
2(PO
4)
3powder mixes according to the weight ratio of 80:10:10 with acetylene black, binding agent PVDF, add appropriate nmp solvent, in the environment of air drying, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, is cut into the pole piece coiling of 60 × 20mm at Na after drying
3zr
2si
2pO
12on pipe outer wall, insert in stainless steel shell shown in shown in Fig. 4 afterwards, drip the sodium perchlorate of 400mL, propene carbonate electrolyte as positive pole simultaneously.
2, get the biphenyl, DME, the sodium metal liquid negative material 10mL that prepare and be injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
3, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 2.8V, and charging by voltage is 3.6V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 16, and can find out that its first all charging capacity can reach 115mAh/g, discharge capacity 109mAh/g, first all coulombic efficiencies are about 95%, and charge and discharge potential plateau is about 3.1 ~ 3.3V.
Embodiment 15
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with Na
0.44mnO
2structure can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, by Na
0.44mnO
2powder mixes with the weight ratio of carbon black according to 80:10, add appropriate trifluoromethyl sulfonate simultaneously, propene carbonate supporting electrolyte is mixed into slurry, then slurry is injected as positive pole in the shell of stainless steel shown in Fig. 4, by ready Na-β, "-Al2O3 earthenware is inserted into stainless steel shell afterwards.
2, get the biphenyl, DME, the sodium metal liquid negative material 10mL that prepare and be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
3, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 2V, and charging by voltage is 3.8V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 17, and can find out that its first all discharge capacity can reach 110mAh/g, charging capacity 109mAh/g, first all coulombic efficiencies are about 99%, and charge and discharge potential range is 2 ~ 3.8V.
Embodiment 16
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with pyrene-DME-sodium metal liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the pyrene-DME-sodium metal liquid positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid negative material prepared, such as biphenyl-DME-sodium metal solution 10mL, be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts the charge and discharge mode of limit capacity to carry out, and discharge voltage is 0.45V, and being charged to voltage is 0.6V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 18, can find out that its discharge capacity can reach 120mAh/g, charging capacity 120mAh/g, and the voltage after ten weeks that circulates is appointed and so obviously do not decayed.
Embodiment 17
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with aphthacene-DME-sodium metal liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the aphthacene-DME-sodium metal liquid positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 2 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that pipe is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in pipe, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharge cut-off voltage is 0.6V, and charge cutoff pressure is 1.3V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 19, can find out that its specific discharge capacity can reach 120mAh/g, charge specific capacity 105mAh/g.
Embodiment 18
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with Na
2s
8what-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 got
2s
8-DMSO liquid positive electrode 10mL is injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid metal negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharge cut-off voltage is 1.5V, and charge cutoff pressure is 2.1V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 20, and can find out that its first all specific discharge capacity can reach 160mAh/g, charge specific capacity 159mAh/g, efficiency for charge-discharge is 99%.Safety experiment is carried out to biphenyl-DME-sodium metal liquid metal negative pole, Figure 21 is that after dripping many sulphions, biphenyl-DME-sodium metal solution is schemed over time, can find out that biphenyl-DME-sodium metal and many sulphions react gentleer from figure, further illustrate the battery safety that biphenyl-DME-sodium metal solution negative pole and many sulphions form higher.
Embodiment 19
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with Na
2s
12what-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 got
2s
12-DMSO liquid positive electrode 10mL is injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the liquid metal negative material prepared, such as biphenyl-DME-sodium metal solution 10mL is injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharge cut-off voltage is 1.6V, and charge cutoff pressure is 2.5V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 22, and can find out that its first all specific discharge capacity can reach 250mAh/g, charge specific capacity 250mAh/g, efficiency for charge-discharge is 99%.
Embodiment 20
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with S-carbon black slurry positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, take sulphur 6mg, carbon black 1mg adds a certain amount of NaSO
3cF
3-DOL-DME solution is mixed into slurry and is injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that pipe is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, and ready aluminium net is inserted into this negative pole liquid as collector.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging by voltage is 2.6V, and charging and discharging currents is 0.2mA.Test result is shown in Figure 23, and can find out that its first all discharge capacity can reach 700mAh/g, charging capacity 550mAh/g, first all coulombic efficiencies are about 79%, and discharge potential platform is about 1.7 ~ 1.9V.When discharge and recharge scope is 1.7 ~ 2.8V, as shown in figure 24, its first all discharge capacity is 360mAh/g to its test result, and charging capacity is 340mAh/g, coulombic efficiency 94%.
Embodiment 21
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with tetramethoxy piperidines-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the tetramethoxy piperidines-PC-sodium perchlorate liquid positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, Na-β "-Al will be got out
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 2.5V, and charging by voltage is 3.6V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 25, and can find out that its first all charging capacity can reach 205mAh/g, discharge capacity 200mAh/g, first all coulombic efficiencies are about 97%, and charge and discharge potential plateau is about 3.1 ~ 3.4V.
Embodiment 22
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with K
3fe (CN)
6what the aqueous solution constructed can the concrete preparation method of charge-discharge battery and charge-discharge performance thereof.
Its concrete preparation method is:
1, the K prepared is got
3fe (CN)
6aqueous solution positive electrode 10mL is injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain energy-storage battery of the present invention
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 2.5V, and charging by voltage is 3.8V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 26, and can find out that its first all charging capacity can reach 68mAh/g, discharge capacity 74mAh/g, first all coulombic efficiencies are about 91%, and charge and discharge potential plateau is about 3.1 ~ 3.3V.
Embodiment 23
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with benzophenone-DME-sodium metal liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the benzophenone-DME-sodium metal solution positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain energy-storage battery of the present invention
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 0.8V, and charging by voltage is 1.5V, and charging and discharging currents is 0.04mA.Test result is shown in Figure 27, and can find out that its first all discharge capacity can reach 300mAh/g, charging capacity 250mAh/g, first all coulombic efficiencies are about 83%, and discharge potential platform is about 0.8 ~ 1V.
Embodiment 24
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with iodo-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the iodo-PC-sodium perchlorate solution positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 2V, and charging by voltage is 3V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 28, and can find out that its first all discharge capacity can reach 200mAh/g, charging capacity 210mAh/g, first all coulombic efficiencies are about 95%, and charge and discharge potential plateau is about 2.8 ~ 3.0V.
Embodiment 25
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with ferrocene-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the ferrocene-PC-sodium perchlorate solution positive electrode 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 2.5V, and charging by voltage is 3.1V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 29, and can find out that its first all charging capacity can reach 200mAh/g, discharge capacity 210mAh/g, first all coulombic efficiencies are about 95%, and charge and discharge potential plateau is about 2.7 ~ 3.0V.
Embodiment 26
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with acenaphthene-DME-sodium metal liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the acenaphthene-DME-sodium metal solution 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 0V, and charging by voltage is 0.65V, and charging and discharging currents is 0.02mA.Test result is shown in Figure 30, and can find out that its first all charging capacity can reach 150mAh/g, charging capacity 130mAh/g, first all coulombic efficiencies are about 86%, and discharge potential platform is about 0.2 ~ 0.3V.
Embodiment 27
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with quinoline woods-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the quinoline woods-PC-sodium perchlorate solution 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na
3zr
2si
2pO
12it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the biphenyl-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na
3zr
2si
2pO
12as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging by voltage is 2.6V, and charging and discharging currents is 0.1mA.Test result is shown in Figure 31, and can find out that its first all discharge capacity can reach 120mAh/g, charging capacity 80mAh/g, first all coulombic efficiencies are about 67%.
Embodiment 28
The present embodiment for illustration of biphenyl-DME-sodium metal liquid metal negative material provided by the present invention, with anthraquinone-PC-sodium perchlorate liquid positive electrode construct can the preparation method of charge and discharge room temperature liquid metal battery, and charge-discharge performance.
Its concrete preparation method is:
1, get the anthraquinone-PC-sodium perchlorate solution 10mL prepared to be injected in the stainless steel case shown in Fig. 4 as positive pole.
2, by ready Na-β "-Al
2o
3it is interior as electrolyte and barrier film that earthenware is inserted into the stainless steel case that liquid positive electrode is housed.
3, get the naphthalene-DME-sodium metal liquid metal negative material 10mL prepared and be injected into above-mentioned Na-β "-Al
2o
3as negative pole in earthenware, ready aluminium net is inserted into this negative pole liquid as collector simultaneously.
4, obtained cell mouth is sealed completely can obtain of the present invention can charge and discharge room temperature liquid metal battery.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.5V, and charging by voltage is 2.6V, and charging and discharging currents is 0.2mA.Test result is shown in Figure 32, and can find out that its first all discharge capacity can reach 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 for illustration of the invertibity of biphenyl-DME-sodium metal liquid metal negative material electrochemical reaction provided by the present invention.
Concrete grammar is:
1, by excessive anthraquinone 5mg and poly(ethylene oxide) in the ratio of 5:1 mix add a certain amount of PC-sodium perchlorate supporting electrolyte simultaneously after be coated in Na-β "-Al
2o
3on potsherd.
2, the liquid metal negative pole getting the NaBP containing 4.1mg drops in bottom button cell shell.
3, Na-the β "-Al of anthraquinone will be coated with
2o
3potsherd is pressed on liquid metal negative pole, tests after buckling bonnet.
The test of battery adopts constant current charge-discharge pattern to carry out, and discharging by voltage is 1.0V, and charging by voltage is 2.7V, and charging and discharging currents is 0.1mA.Test result is shown in that Figure 33 specific capacity obtains according to NaBP Mass Calculation, can find out that its first all discharge capacity is 76mAh/g, charging capacity 65mAh/g, which illustrates the high reversible that NaBP stores up sodium.
In the various embodiments described above; can the preparation method of charge and discharge room temperature liquid metal battery and performance be illustrated provided by the invention; although in various embodiments, biphenyl-DME-sodium metal is illustrated as liquid metal negative material, protection scope of the present invention can not be limited with this.Of the present invention can the negative material of charge and discharge room temperature liquid metal battery can comprise in the liquid metal negative material that the embodiment of the present invention 1 provides any one.
The liquid metal negative material provided in the above embodiment of the present invention has the mobility of liquid, good electron conduction and ionic conductivity, low current potential, high fail safe and good wetting property, this material is had the characteristic of high-energy-density, long circulation life as the battery that negative pole is prepared into, can be used for the storage that the power station such as solar energy, wind energy exports electric energy.
What the embodiment of the present invention provided can the structure of charge and discharge room temperature liquid metal battery, can cylindrical battery as shown in Figure 4 as described in the various embodiments described above, it can also 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, what provide with embodiment 30-embodiment 33 pairs of embodiment of the present invention respectively can the structure of charge and discharge room temperature liquid metal battery be described in detail again.
Embodiment 30
The present embodiment is in order to cylindricly can the structure of charge and discharge room temperature liquid metal battery being described of providing the embodiment of the present invention.
As shown in Figure 4, Fig. 4 is the structural representation of cylindrical battery.The pictorial diagram of cylindrical battery can be as shown in figure 34.As shown in Figure 4, cylindrical battery can comprise: Stainless Steel Shell and solid electrolyte tube;
Described solid electrolyte tube is contactless to be nested in described Stainless Steel Shell, and the confined space between described Stainless Steel Shell inwall and described solid electrolyte tube outer wall is used for accommodating described liquid positive electrode; For accommodating described liquid metal negative material in described solid electrolyte tube.
During electric discharge, electronics arrives positive pole by external circuit from negative pole and is reduced by positive active material, and sodium ion arrives positive pole by solid electrolyte from negative pole simultaneously.Charging process is then, and electronics arrives negative pole from positive pole, and ion also arrives negative pole from positive pole by solid electrolyte simultaneously.
Embodiment 31
The present embodiment can the structure of charge and discharge room temperature liquid metal battery be described in order to the Dual-flow that provides the embodiment of the present invention.
As shown in Figure 5, 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, described liquid positive electrode accommodating in positive pole fluid reservoir is pumped in described positive pole space, described negative pole space is connected with described negative pole fluid reservoir, is pumped in described negative pole space by described liquid metal negative material accommodating in negative pole fluid reservoir by a pump.Operation principle to cylindric can charge and discharge room temperature liquid metal battery similar, repeat no more.
Embodiment 32
The present embodiment can the structure of charge and discharge room temperature liquid metal battery be described in order to single liquid stream of providing the embodiment of the present invention.
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, pump in described positive pole space by described pump by described liquid positive electrode accommodating in positive pole fluid reservoir, described negative pole space is used for accommodating described liquid metal negative 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 structure of charge and discharge room temperature liquid metal battery be described in order to the flat board that provides the embodiment of the present invention.
As shown in Figure 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, and described positive pole space is used for accommodating described liquid positive electrode, and described negative pole space is used for accommodating described liquid metal negative material.Operation principle to cylindric can charge and discharge room temperature liquid metal battery similar, repeat no more.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection range be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (17)
1. a liquid metal negative material, is characterized in that, described negative material is the blackish green liquid that the mixing of alkali metal, aromatic compound and ether solvent generates;
Wherein, described alkali metal be in sodium metal, lithium metal or metallic potassium any one or multiple;
Described aromatic compound be biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene derivative in any one or multiple;
Described ether solvent comprises ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol 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-dioxolanes, dimethoxymethane, 1,2-dimethoxy propane, dioxolane, 1, in 4-dioxane, oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide (DMSO), sulfolane or dimethyl sulfone any one or multiple.
2., as a preparation method for above-mentioned liquid metal negative material according to claim 1, it is characterized in that, described method comprises:
In the protective atmosphere of argon gas, alkali metal and aromatic compound are added in ether solvent according to certain mol proportion, leave standstill, obtain described liquid metal negative material;
Wherein, described alkali metal be in sodium metal, lithium metal or metallic potassium any one or multiple;
Described aromatic compound be biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene derivative in any one or multiple;
Described ether solvent comprises ether, methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol 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-dioxolanes, dimethoxymethane, 1,2-dimethoxy propane, dioxolane, 1, in 4-dioxane, oxirane, expoxy propane, 1,1-diethoxyethane, dimethyl sulfoxide (DMSO), sulfolane or dimethyl sulfone any one or multiple.
3. one kind comprise liquid metal negative material described in the claims 1 can charge and discharge room temperature liquid metal battery.
4. according to claim 3 can charge and discharge room temperature liquid metal battery, it is characterized in that, describedly can also to comprise 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 comprises the Na for conducts sodium ions, lithium ion or potassium ion
3zr
2si
2pO
12pottery, Na-β "-Al
2o
3pottery, K-β "-Al
2o
3pottery, Li
7la
3zr
2o
12pottery or Li
10geP
2s
12any one in pottery.
5. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterized in that, the preparation method of described slurry positive electrode comprises:
The pressed powder of positive active material, carbon dust are mixed by certain mass ratio, adds a certain amount of supporting electrolyte and stir, namely obtain described liquid positive electrode;
Wherein, described positive active material comprises: Na
0.44mnO
2, NaTi
2(PO
4)
3, Na
3v
2(PO
4) 3, Na
0.8li
0.1ni
0.25mn
0.65o
2, NaMg
0.1ni
0.4mn
0.2ti
0.3o
2, S, K
3fe (CN)
6, Na
4fe (CN)
6, FePO
4in any one or more.
6. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterized in that, the preparation method of described slurry positive electrode comprises:
Liquid positive electrode, carbon dust are mixed by certain mass ratio, adds a certain amount of supporting electrolyte and stir, namely obtain described liquid positive electrode.
7. according to claim 4 or 6 can charge and discharge room temperature liquid metal battery, it is characterized in that, described liquid positive electrode is:
So that in the derivative of the derivative of the derivative of the derivative of 1,4-benzoquinone, 1,4-benzoquinone, anthraquinone, anthraquinone, acenaphthenequinone, acenaphthenequinone, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, with glycol dimethyl ether, propene carbonate or tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE, any one or more is mixed into solvent, the liquid of formation.
8. according to claim 4 or 6 or 7 arbitrary described can charge and discharge room temperature liquid metal battery, it is characterized in that, the preparation method of described liquid positive electrode comprises:
So that in the derivative of the derivative of the derivative of the derivative of the 1,4-benzoquinone of 0.1 ~ 5mol, 1,4-benzoquinone, anthraquinone, anthraquinone, acenaphthenequinone, acenaphthenequinone, phenanthrenequione or phenanthrenequione, any one or more is mixed into solute, be dissolved in 1L with glycol dimethyl ether, propene carbonate, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE any one or more mixing solvent in, add a certain amount of supporting electrolyte, namely obtain described liquid positive electrode.
9. according to claim 4 or 6 can charge and discharge room temperature liquid metal battery, it is characterized in that, described liquid positive electrode is:
With arbitrary for solute in benzophenone, acenaphthene, aphthacene, pentacene or pyrene, with glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE, any one or more is mixed into solvent, the liquid of formation.
10. according to claim 4 or 6 or 9 arbitrary described can charge and discharge room temperature liquid metal battery, it is characterized in that, the preparation method of described liquid positive electrode comprises:
So that in the benzophenone of 0.1 ~ 5mol, acenaphthene, aphthacene, pentacene or pyrene, any one or more is mixed into solute, be dissolved in the solvent of any one or more mixing of the glycol dimethyl ether of 1L, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide or 1-METHYLPYRROLIDONE, add a certain amount of alkali metal, leave standstill, namely obtain described liquid positive electrode.
11. according to claim 4 or 6 can charge and discharge room temperature liquid metal battery, it is characterized in that, described liquid positive electrode is:
With Na
2s
xfor solute, with dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide, 1-METHYLPYRROLIDONE or water, any one or more is mixed into the solution that solvent is formed; Wherein, 3≤x≤12.
12. according to claim 4 or 6 or 11 can charge and discharge room temperature liquid metal battery, it is characterized in that, the preparation method of described liquid positive electrode comprises:
According to Na
2the mol ratio of S/S=1/ (x-1) is by Na
2s and S adds in the solvent of any one or more mixing of dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl formamide, 1-METHYLPYRROLIDONE or water, and add a certain amount of supporting electrolyte and be stirred to and dissolve completely, namely obtain described liquid positive electrode;
Wherein, 3≤x≤12.
13. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterized in that, described can charge and discharge room temperature liquid metal battery be cylindrical battery, comprising:
Stainless Steel Shell and solid electrolyte tube;
Described solid electrolyte tube is contactless to be nested in described Stainless Steel Shell, and the confined space between described Stainless Steel Shell inwall and described solid electrolyte tube outer wall is used for accommodating described liquid positive electrode; For accommodating described liquid metal negative material in described solid electrolyte tube.
14. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterized in that, described can charge and discharge room temperature liquid metal battery be double flow battery, comprising:
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, described liquid positive electrode accommodating in positive pole fluid reservoir is pumped in described positive pole space, described negative pole space is connected with described negative pole fluid reservoir, is pumped in described negative pole space by described liquid metal negative material accommodating in negative pole fluid reservoir by a pump.
15. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterized in that, described can charge and discharge room temperature liquid metal battery be single flow battery, comprising:
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, pump in described positive pole space by described pump by described liquid positive electrode accommodating in positive pole fluid reservoir, described negative pole space is used for accommodating described liquid metal negative material.
16. according to claim 4 can charge and discharge room temperature liquid metal battery, it is characterized in that, described can charge and discharge room temperature liquid metal battery be flat metal battery, comprising:
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, and described positive pole space is used for accommodating described liquid positive electrode, and described negative pole space is used for accommodating described liquid metal negative material.
As described in 17. 1 kinds of claims as arbitrary in the claims 3-16 can the purposes of charge and discharge room temperature liquid metal battery, it is characterized in that, describedly can be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station by charge and discharge room temperature liquid metal battery.
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| PCT/CN2015/081807 WO2016019765A1 (en) | 2014-08-06 | 2015-06-18 | Liquid metal cathode material and room-temperature liquid metal battery, and preparation method thereof and usage thereof |
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| CN201410383865.0A CN105098140B (en) | 2014-08-06 | 2014-08-06 | Liquid metal negative material and room temperature liquid metal battery, preparation method and purposes |
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| CN105489880A (en) * | 2015-12-31 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Composite sodium-storage positive electrode for solid-state secondary sodium battery and preparation method for composite sodium-storage positive electrode |
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Also Published As
| Publication number | Publication date |
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| WO2016019765A1 (en) | 2016-02-11 |
| CN105098140B (en) | 2016-08-24 |
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