CN105742727A - Secondary battery, application and preparation method of negative electrode of secondary battery - Google Patents
Secondary battery, application and preparation method of negative electrode of secondary battery Download PDFInfo
- Publication number
- CN105742727A CN105742727A CN201410749445.XA CN201410749445A CN105742727A CN 105742727 A CN105742727 A CN 105742727A CN 201410749445 A CN201410749445 A CN 201410749445A CN 105742727 A CN105742727 A CN 105742727A
- Authority
- CN
- China
- Prior art keywords
- liquid metal
- conductive liquid
- solid electrolyte
- ether
- secondary cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
The invention discloses a secondary battery, an application and a preparation method of a negative electrode of the secondary battery. The secondary battery comprises solid metal sodium or lithium or potassium, conductive liquid metal, a solid electrolyte, a positive electrode material and a battery shell, wherein the solid metal sodium or lithium or potassium and the conductive liquid metal are accommodated in a solid electrolyte tube formed by the solid electrolyte; or the part between the battery shell and the solid electrolyte is filled with the solid metal sodium or lithium or potassium and the conductive liquid metal; the solid metal sodium or lithium or potassium and the conductive liquid metal form a high-capacity negative electrode of the secondary battery; the part between the battery shell and the solid electrolyte is filled with the positive electrode material to form a positive electrode of the secondary battery; and the conductive liquid metal comprises a liquid generated by mixing any one or more of metal sodium, lithium and potassium and an aromatic compound and an ether solvent.
Description
Technical field
The present invention relates to cell art, the preparation method particularly relating to a kind of secondary cell, purposes and negative pole thereof.
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 undulatory property and the intermittent instability that result in electrical network of solar energy, wind energy, 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 demand management, eliminates 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, electrochemical energy storage etc..Various energy storage technologies have respective use condition and advantage, all in positive research and development and demonstration stage.Wherein energy storage electrochmical power source such as sodium-sulphur battery, all-vanadium flow battery, lithium ion battery have had some to demonstrate as extensive energy storage device.
But sodium-sulphur battery needs to run under 300 degree of high temperature, the directly use of molten metal sodium and sulfur result in this battery and there is serious etching problem and potential safety hazard.Vanadium ion used by all-vanadium flow battery belongs to extremely toxic substance and resource-constrained, the problem that additionally there is the phase counterdiffusion of both positive and negative polarity active substance in its running, and the energy density of this energy-storage battery is not high.Lithium ion battery has good performance as extensive energy-storage battery, but the manufacturing cost of lithium-ion energy storage battery is high.Therefore not a kind of energy-storage battery can meet the comprehensive requirement such as low cost, good, the abundant raw materials of safety at present.The battery of metallic sodium or lithio has the advantage of high-energy-density, dendrite and side reaction all can be had when but metallic sodium or lithium carry out discharge and recharge inside organic electrolyte cell to generate, we have proposed a kind of room temperature battery design that can overcome dendritic growth, side reaction and obtain metal battery high-energy-density at this.
Summary of the invention
The preparation method embodiments providing a kind of novel secondary cell, purposes and negative pole thereof.By the metallic sodium of solid-state or lithium or potassium are placed in conductive liquid metal negative pole, greatly improving the capacity of conductive liquid metal negative pole thus improve the energy density of battery, also solving that interface resistance between the metal negative electrode of solid-state and solid electrolyte is big, the problem of dendritic growth and side reaction simultaneously.The secondary cell of the present invention has the characteristic of high-energy-density, long circulation life, can be used for the storage of the power station such as solar energy, wind energy output electric energy.
First aspect, embodiments provides a kind of secondary cell, and described secondary cell includes the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, solid electrolyte, positive electrode and battery container；
The metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal are placed in described solid electrolyte tube, or, the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal are filled between described battery container and described solid electrolyte, and the metallic sodium of described solid-state or lithium or potassium constitute the negative pole of described secondary cell together with conductive liquid metal；
Described conductive liquid metal includes in metallic sodium, lithium, potassium any one or several and mixes the liquid generated with aromatic compound and ether solvent；
Described positive electrode is filled between described battery container and described solid electrolyte, forms the positive pole of described secondary cell；
Wherein, described positive electrode includes many sulphions solution, anthraquinone solution, benzoquinone solution, iodine solution, benzophenone solution, tetramethoxy piperidine oxide TEMPO solution or Na0.44MnO2、NaTi2(PO4)3、Na3V2(PO4)3、Na0.8Li0.1Ni0.25Mn0.65O2、NaMg0.1Ni0.4Mn0.2Ti0.3O2, any one or more slurry constituted with carbon dust in S.
Preferably, described secondary cell is cylindrical battery；
Described solid electrolyte is tubulose, houses and in described battery container；
The metallic sodium of described solid-state or lithium or potassium are placed in described solid electrolyte tube, and conductive liquid metal is filled between metallic sodium or lithium or potassium and solid electrolyte.
Preferably, described secondary cell is double flow battery, and described battery also includes: positive pole fluid reservoir, negative pole fluid reservoir and two pumps；
Described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, wherein said positive pole space is connected with described positive pole fluid reservoir, is pumped in described positive pole space by described positive electrode accommodating in positive pole fluid reservoir by a pump；Described negative pole space is connected with described negative pole fluid reservoir, and in described negative pole fluid reservoir, the metallic sodium of accommodating solid-state or lithium or potassium and described conductive liquid metal, pumped into described conductive liquid metal accommodating in negative pole fluid reservoir in described negative pole space by a pump.
Preferably, described secondary cell is single flow battery, and described battery also includes: positive pole fluid reservoir and pump；
Described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, wherein said positive pole space is connected with described positive pole fluid reservoir, pumping in described positive pole space by described pump by described positive electrode accommodating in positive pole fluid reservoir, described negative pole space is used for housing the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal.
Preferably, described secondary cell is flat plate cell；
Described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, described positive pole space is used for housing described positive electrode, and described negative pole space is used for housing the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal material.
Preferably, described aromatic compound be in the derivant of biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene any one or multiple；
Described ether solvent include 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 any one or multiple.
Preferably, the preparation method of described conductive liquid metal includes:
In the protective atmosphere of argon, alkali metal and aromatic compound are added in ether solvent according to certain mol proportion, stands, obtain described conductive liquid metal negative material；
Wherein, described alkali metal be in metallic sodium, lithium metal or metallic potassium any one or multiple；
Described aromatic compound be in the derivant of biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene any one or multiple；
Described ether solvent include 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 any one or multiple.
Preferably, the preparation method of described high power capacity negative pole includes:
In the protective atmosphere of argon; above-mentioned conductive liquid metal is injected in solid electrolyte tube; afterwards excessive solid metallic sodium or lithium or potassium are inserted in conductive liquid metal; from solid metallic, draw negative wire afterwards, after being sealed by the solid electrolyte mouth of pipe, after static two hours, described high power capacity negative pole can be obtained；
Preferably, described solid electrolyte includes the Na for conducts sodium ions, lithium ion or potassium ion3Zr2Si2PO12Pottery, Na-β "-Al2O3Pottery, K-β "-Al2O3Pottery, Li7La3Zr2O12Pottery or Li10GeP2S12Any one in pottery.
Second aspect, embodiments providing the purposes of secondary cell described in a kind of above-mentioned first aspect, described secondary cell is for the extensive energy storage device of solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
The third aspect, the preparation method embodiments providing the negative pole of secondary cell described in a kind of above-mentioned first aspect, including:
In the protective atmosphere of argon, conductive liquid metal is injected in the solid electrolyte tube that solid electrolyte is constituted, or is injected between battery container and described solid electrolyte；
Excessive solid metallic sodium or lithium or potassium are inserted in conductive liquid metal；
Negative wire is drawn from solid metallic；
By after the sealing of the solid electrolyte mouth of pipe static two hours, namely obtain described negative pole.
The metallic sodium of solid-state or lithium or potassium are placed in conductive liquid metal negative pole by the secondary cell that the embodiment of the present invention provides, greatly improve the energy density of conductive liquid metal battery, there is high safety and cheap cost, it is possible to be operated in room temperature in the temperature range of 150 DEG C.Can being applied to prepare the rich material resources of secondary cell of the present invention, the specific energy of battery is high, has extended cycle life, and 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 cylindrical battery configuration schematic diagram that Fig. 1 provides for the embodiment of the present invention；
The double flow battery structural representation that Fig. 2 provides for the embodiment of the present invention；
The single flow battery structural representation that Fig. 3 provides for the embodiment of the present invention；
The flat plate cell structural representation that Fig. 4 provides for the embodiment of the present invention；
The Symmetrical cells charge-discharge performance curve of the conductive liquid metal composition that Fig. 5 provides for the embodiment of the present invention；
Charge-discharge performance curve metallic sodium being immersed in conductive liquid metal Symmetrical cells that Fig. 6 provides for the embodiment of the present invention；
Electrochemical impedance spectroscopy metallic sodium immersed in conductive liquid metal Symmetrical cells after discharge and recharge that Fig. 7 provides for the embodiment of the present invention；
The Raman collection of illustrative plates that metallic sodium is immersed metallic sodium surface and conductive liquid metal afterwards in conductive liquid metal that Fig. 8 provides for the embodiment of the present invention；
The battery charging and discharging performance map of the secondary cell that Fig. 9 provides for the embodiment of the present invention.
The charge-discharge performance figure of the battery that solid metallic sodium that Figure 10 provides for the embodiment of the present invention, conductive liquid metal, solid electrolyte, tetramethoxy piperidine oxide TEMPO liquid positive electrode are constituted；
Solid metallic sodium, conductive liquid metal, solid electrolyte, Na during Figure 11 provide for the embodiment of the present invention 70 DEG C2S8The charge-discharge performance figure of the battery that liquid positive electrode is constituted.
Detailed description of the invention
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 present embodiment is in order to illustrate the structure of secondary cell provided by the invention.
Secondary cell provided by the invention includes the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, solid electrolyte, positive electrode and battery container:
The metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal are placed in described solid electrolyte, or, the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal are filled between described battery container and described solid electrolyte；The metallic sodium of described solid-state or lithium or potassium constitute the negative pole of described secondary cell together with conductive liquid metal；This negative pole design ratio only has higher capacity with conductive liquid metal as negative pole thus greatly improving the energy density of battery；It is placed in conductive liquid metal by the metallic sodium of solid-state can to make the electrical conductivity that conductive liquid metal keeps higher simultaneously；Additionally solid metallic sodium or lithium or potassium are placed in conductive liquid metal and also solve the problem that alkali metal has side reaction generation and dendritic growth inside common organic solvents.
Described positive electrode is filled between described battery container and described solid electrolyte, forms the positive pole of described secondary cell；
Wherein, described positive electrode includes many sulphions solution, anthraquinone solution, benzoquinone solution, iodine solution, benzophenone solution, tetramethoxy piperidine oxide solution or Na0.44MnO2、NaTi2(PO4)3、Na3V2(PO4)3、Na0.8Li0.1Ni0.25Mn0.65O2、NaMg0.1Ni0.4Mn0.2Ti0.3O2, any one or more slurry constituted with carbon dust in S；
Described conductive liquid metal includes in metallic sodium, lithium, potassium any one or several and mixes the liquid generated with aromatic compound and ether solvent；
Described aromatic compound be in the derivant of biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene any one or multiple；
Described ether solvent include 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 any one or multiple；
Described solid electrolyte includes the Na for conducts sodium ions, lithium ion or potassium ion3Zr2Si2PO12Pottery, Na-β "-Al2O3Pottery, K-β "-Al2O3Pottery, Li7La3Zr2O12Pottery or Li10GeP2S12Any one in pottery.
The specific configuration of secondary cell of the present invention can be various, such as cylindrical battery, double flow battery, single flow battery or flat plate cell, and rear extended meeting is described separately these heteroid architectural features with multiple embodiments.
Below to adopt metallic sodium to be placed in be equipped with in the solid electrolyte tube of conductive liquid metal the negative pole being constituted secondary cell that the operation principle of secondary cell of the present invention is described.
When secondary cell discharges, the conductive liquid metal of negative pole loses electronics and is oxidized to biphenyl (formula 1), and electronics arrives positive pole from external circuit and reduced by positive electrode；Sodium ion in the conductive liquid metal of negative pole then arrives positive pole to maintain charge balance by solid electrolyte, after conductive liquid metal is oxidized to biphenyl, the metallic sodium of solid-state is reduced again (formula 2), then discharge process proceeds, until metallic sodium is completely consumed whole discharge process and just can terminate.It is below discharge process reaction equation:
Charging process is then contrary with discharge process, and electronics arrives negative pole ion simultaneously from positive pole and also arrives negative pole by biphenyl reduction from positive pole by solid electrolyte.After the sodium ion in conductive liquid metal reaches capacity, the sodium ion in conductive liquid metal continues to be reduced to solid metallic sodium, is deposited on collector or battery container.
The secondary cell of the present invention can be operated in room temperature in the temperature range of 150 DEG C, this structural design is adopted to improve the capacity of conductive liquid metal negative pole, conductive liquid metal is filled in the design between metallic sodium and solid electrolyte simultaneously, solves solid metallic negative pole and solid electrolyte interface resistance is very big and alkali metal has dendritic growth and the problem of side reaction generation.
Embodiment 2
The present embodiment is in order to illustrate the structure of the cylindrical battery described in above-described embodiment 1.
Fig. 1 is the structural representation of cylindrical battery.As it is shown in figure 1, cylindrical battery may include that the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, battery container, positive electrode and solid electrolyte tube；
Described solid electrolyte tube is contactless to be nested in described battery container, and the confined space between described battery container inwall and described solid electrolyte tube outer wall is used for housing described positive electrode；It is used for housing the negative material of the metallic sodium of described conductive liquid metal and solid-state or lithium or potassium composition in described solid electrolyte tube.
When secondary cell discharges, the conductive liquid metal of negative pole loses electronics and is oxidized to biphenyl (formula 1), and electronics arrives positive pole from external circuit and reduced by positive electrode；Sodium ion in the conductive liquid metal of negative pole then arrives positive pole to maintain charge balance by solid electrolyte, after conductive liquid metal is oxidized to biphenyl, the metallic sodium of solid-state is reduced again (formula 2), then discharge process proceeds, until metallic sodium is completely consumed whole discharge process and just can terminate.Charging process is then contrary with discharge process, and electronics arrives negative pole ion simultaneously from positive pole and also arrives negative pole by conductive liquid metal reduction from positive pole by solid electrolyte.After the sodium ion in conductive liquid metal reaches capacity, the sodium ion in conductive liquid metal continues to be reduced to solid metallic sodium, is deposited on collector or battery container.
Embodiment 3
The present embodiment is in order to illustrate the structure of the double flow battery described in above-described embodiment 1.
Fig. 2 is the structural representation of double flow battery.As in figure 2 it is shown, double flow battery may include that the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, battery container, positive electrode, solid electrolyte tube, positive pole fluid reservoir, negative pole fluid reservoir and two pumps；
Described solid electrolyte is as barrier film, described battery container is divided into airtight positive pole space and negative pole space, wherein said positive pole space is connected with described positive pole fluid reservoir, is pumped in described positive pole space by described positive electrode accommodating in positive pole fluid reservoir by a pump；Described negative pole space is connected with described negative pole fluid reservoir, and in described negative pole fluid reservoir, the metallic sodium of accommodating solid-state or lithium or potassium and described conductive liquid metal, pumped into described conductive liquid metal accommodating in negative pole fluid reservoir in described negative pole space by a pump.The operation principle of double flow battery is similar to cylindrical battery, repeats no more.
Embodiment 4
The present embodiment is in order to illustrate the structure of the single flow battery described in above-described embodiment 1.
Fig. 3 is the structural representation of single flow battery.As it is shown on figure 3, single flow battery may include that the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, battery container, positive electrode, solid electrolyte tube, positive pole fluid reservoir and pump；
Described solid electrolyte is as barrier film, described battery container is divided into airtight positive pole space and negative pole space, wherein said positive pole space is connected with described positive pole fluid reservoir, pumping in described positive pole space by described pump by described positive electrode accommodating in positive pole fluid reservoir, described negative pole space is used for housing the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal.The operation principle of single flow battery is similar to cylindrical battery, repeats no more.
Embodiment 5
The present embodiment is in order to illustrate the structure of the flat plate cell described in above-described embodiment 1.
Fig. 4 is the structural representation of flat plate cell.As shown in Figure 4, described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, and described positive pole space is used for housing described positive electrode, and described negative pole space is used for housing the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal material.The operation principle of flat plate cell is similar to cylindrical battery, repeats no more.
In each embodiment above-mentioned, battery container is preferably Stainless Steel Shell, and positive electrode can include the one in liquid positive electrode or slurry positive electrode.The preparation method with embodiment 6, the conductive liquid metal described in the embodiment of the present invention 1 being described separately below, and it is described separately the preparation method of positive electrode described in the embodiment of the present invention 1 with embodiment 7-10.
Embodiment 6
The present embodiment is in order to illustrate the preparation method of conductive liquid metal in above-described embodiment 1.
Described method includes:
In the protective atmosphere of argon, alkali metal and aromatic compound are added in ether solvent according to certain mol proportion, stands, obtain described conductive liquid metal；
Wherein, described alkali metal be in metallic sodium (Na), lithium metal (Li) or metallic potassium (K) any one or multiple；
Described aromatic compound be in the derivant of biphenyl (BP), connection benzene derivate, naphthalene (NP), naphthalene derivatives, anthracene or anthracene any one or multiple；
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 include 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, in 4-dioxane, oxirane, expoxy propane, 1,1-diethoxyethane any one or multiple.Wherein it is preferably, the one in DME, DEGDME or TEGDME.
Alkali metal, aromatic compound react after mixing in ether solvent, are mixed into example with sodium, biphenyl and DME solvent below and illustrate.
Course of reaction is such as shown in following formula 3:
The conductive liquid metal that the embodiment of the present invention provides is used as a part for secondary battery cathode material of the present invention, there is the mobility of liquid, good electronic conduction and ionic conductivity, low current potential, high safety and good wetting property, with low cost, rich material resources, has the characteristic of high-energy-density, long circulation life using this material as battery cathode.
Embodiment 7
The present embodiment is in order to illustrate the preparation method of positive electrode in above-described embodiment 1.
Described positive electrode is liquid positive electrode, particularly as follows:
In the derivant of 1,4-benzoquinone, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, the derivant of acenaphthenequinone, phenanthrenequione or phenanthrenequione or tetramethyl piperidine nitrogen oxides arbitrary for solute, be simultaneously introduced, so that glycol dimethyl ether, Allyl carbonate or tetraethyleneglycol dimethyl ether are arbitrary, the liquid that a certain amount of trifluoromethyl sulfonate is constituted as supporting electrolyte for solvent.
Its preparation method can be:
In the derivant of the 1,4-benzoquinone of 0.1～3mol, the derivant of 1,4-benzoquinone, anthraquinone, the derivant of anthraquinone, acenaphthenequinone, the derivant of acenaphthenequinone, phenanthrenequione or phenanthrenequione arbitrary for solute, be dissolved in 1L with in the arbitrary solvent of glycol dimethyl ether, Allyl carbonate or tetraethyleneglycol dimethyl ether, add a certain amount of trifluoromethyl sulfonate supporting electrolyte, namely obtain described liquid positive electrode.
Such as in a specific example, for anthraquinone-Allyl carbonate-trifluoromethyl sulfonate liquid positive electrode, its concrete preparation process is:
Weigh anthraquinone 2.08g and be dissolved in the propylene carbonate solvent of 10mL, be simultaneously introduced 1.4g trifluoromethyl sulfonate as supporting electrolyte, stir to being completely dissolved and can obtain required liquid positive electrode.
Embodiment 8
The present embodiment is in order to illustrate the preparation method of positive electrode in above-described embodiment 1.
Described positive electrode is liquid positive electrode, particularly as follows:
With tetramethoxy piperidine oxide TEMPO for solute, it is simultaneously introduced a certain amount of trifluoromethyl sulfonate as supporting electrolyte, the liquid of composition using Allyl carbonate for solvent.
Its preparation method can be:
The tetramethoxy piperidines nitrogen oxides of 1～3mol is dissolved in the propylene carbonate solvent of 1L, is simultaneously introduced a certain amount of trifluoromethyl sulfonate supporting electrolyte, stand and within 1 hour, namely obtain described liquid positive electrode.
Embodiment 9
The present embodiment is in order to illustrate the preparation method of positive electrode in above-described embodiment 1.
Described positive electrode is liquid positive electrode, particularly as follows:
In benzophenone, acenaphthene, aphthacene, Benzo[b or pyrene arbitrary for solute, arbitrary for solvent with glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether, the liquid of composition.
Its preparation method can be:
In the benzophenone of 0.1～5mol, acenaphthene, aphthacene, Benzo[b or pyrene arbitrary for solute, it is 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, stand, namely obtain described liquid positive electrode.
Such as in a specific example, for 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 of 160mg as additive, stir to being completely dissolved and can obtain required liquid positive electrode.
Embodiment 10
The present embodiment is in order to illustrate the preparation method of positive electrode in above-described embodiment 1.
Described positive electrode is liquid positive electrode, particularly as follows:
With Na2SxFor solute, with the arbitrary solution constituted for solvent of dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or water.
Its preparation method includes:
According to Na2The mol ratio of S/S=1/ (x-1) is by Na2S and S adds in dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether or the arbitrary solvent of water, and adds the stirring of a certain amount of supporting electrolyte to being completely dissolved, and namely obtains described liquid positive electrode.
Such as in a specific example, with Na2Sx-DMSO liquid positive electrode is example, and its concrete preparation process is:
According to Na2The mol ratio of S/S=1/ (x-1) weighs appropriate Na2S and S joins in dimethyl sulfoxide (DMSO) solution, is simultaneously introduced a certain amount of trifluoromethyl sulfonate and can obtain required liquid positive electrode as supporting electrolyte stirring to being completely dissolved.This liquid positive electrode has good dissolubility, the Na such as prepared in this approach2S8With Na2S4Dissolubility be all higher than 1mol/L.
Embodiment 11
The present embodiment is in order to illustrate the preparation method of positive electrode in above-described embodiment 1.
Described positive electrode is slurry positive electrode, and its preparation method includes:
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、FePO4Deng in the pressed powder of any one or more positive active material, carbon dust press certain mass than mix homogeneously, add a certain amount of supporting electrolyte and be stirred, namely obtaining described liquid positive electrode.
Embodiment 12
The present embodiment is in order to illustrate the preparation method of positive electrode in above-described embodiment 1.
Described positive electrode is slurry positive electrode, and its preparation method includes:
Any one the liquid positive electrode provide above-described embodiment 7 or embodiment 8 or embodiment 9 and carbon dust than mix homogeneously by certain mass, add a certain amount of supporting electrolyte and are stirred, namely obtaining described positive electrode.
Embodiment 13
The Symmetrical cells that the present embodiment forms for conductive liquid metal as electrode, illustrates the charge-discharge performance of conductive liquid metal material provided by the invention.
In the present embodiment, Symmetrical cells be configured to cylindrical battery, accommodating 1 milliliter of 1mol/L conductive liquid metal in solid electrolyte tube, the space between electrolytic tube and battery container is accommodating 1 milliliter of 1mol/L conductive liquid metal also.Carrying out constant current charge-discharge, charging voltage platform is close to 0.2V as shown in Figure 5, the close-0.2V of discharge platform, and the polarizing voltage between discharge and recharge is 0.4V.The test specification of charge-discharge performance conductive liquid metal of the present invention has the electrochemical reversibility of height, can carry out charge and discharge cycles.
Embodiment 14
The Symmetrical cells that the present embodiment forms for conductive liquid metal and metallic sodium as electrode, in order to illustrate metallic sodium dissolving deposition process in the conductive liquid metal that the embodiment of the present invention provides.
In the present embodiment, Symmetrical cells be configured to cylindrical battery, accommodating metallic sodium and the space filled conductive liquid metal between metallic sodium and solid electrolyte tube in solid electrolyte tube, space between solid electrolyte tube and battery container is accommodating metallic sodium and conductive liquid metal also, carry out constant current charge-discharge, limit capacity 3 MAH afterwards.As shown in Figure 6, dissolving that metallic sodium can be reversible in this liquid and deposition, its discharge platform is at-0.1V, and charging platform is 0.1V；Discharge and recharge polarizing voltage is 0.2V, polarization (0.4V less than conductive liquid metal Symmetrical cells, as described in Example 13), the less reason that polarizes be the solid metallic sodium being placed in conductive liquid metal can supplement sodium in conductive liquid metal reduce the electrical conductivity keeping liquid metal higher；The resistance of the electrochemical impedance spectroscopy display battery shown in Fig. 7 does not have to be increased with circulation, and this describes and does not generate solid electrolyte interface (solidelectrolyteinterface, SEI) film and not side reaction generation on metallic sodium surface；Raman spectrum shown in Fig. 8 also illustrate that excessive metallic sodium is immersed in conductive liquid metal and does not have side reaction generation.It is based on this, can realize in the embodiment of the present invention 1, including the secondary cell that the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, solid electrolyte, positive electrode and battery container are constituted.
Embodiment 15
The present embodiment is in order to comparative illustration: the battery that solid metallic sodium, conductive liquid metal, solid electrolyte, positive electrode and the battery container that the embodiment of the present invention provides is constituted, with the difference of the discharge capacity of the cell only constituted with conductive liquid metal, solid electrolyte, positive electrode and battery container.
In the embodiment of the present invention, battery 1 be configured in electrolytic tube accommodating metallic sodium, and between metallic sodium and the space of electrolytic tube filled conductive liquid metal, the space between electrolytic tube and the battery container of cylindrical battery is equipped with excessive Na2S8Liquid positive electrode, the discharge capacity of battery depends on negative pole.Carry out constant current charge-discharge.Battery 2 be configured in electrolytic tube only accommodating conductive liquid metal, the space between electrolytic tube and the battery container of cylindrical battery houses excessive Na2S8Liquid positive electrode, the discharge capacity of battery depends on negative pole.Carry out constant current charge-discharge.Fig. 9 is the performance comparison figure of both batteries.It can be seen that adopting the electricity that battery 1 is released is 8mAh, far above the electricity 4mAh adopting battery 2 to release.
Embodiment 16
The present embodiment is in order to illustrate the battery charging and discharging performance that solid metallic sodium, conductive liquid metal, solid electrolyte, tetramethoxy piperidine oxide (TEMPO) liquid positive electrode are constituted.
Battery be configured in electrolytic tube accommodating metallic sodium, and filled conductive liquid metal between metallic sodium and the space of electrolytic tube, the space between electrolytic tube and the battery container of cylindrical battery is equipped with tetramethoxy piperidine oxide (TEMPO) the liquid positive electrode of 1 milliliter of 1mol/L.Battery is carried out constant current charge-discharge, and voltage range is 2.5 to 3.6V.Figure 10 is its charging and discharging curve, it can be seen that the discharge platform of battery is 3.2V, and charging platform is 3.4V, and platform capacity is about 170mAh/g.
Embodiment 17
The present embodiment is in order to illustrate solid metallic sodium, conductive liquid metal, solid electrolyte, Na at 70 DEG C2S8The battery charging and discharging performance that liquid positive electrode is constituted.
Battery be configured in electrolytic tube accommodating metallic sodium, and filling the conductive liquid metal being made up of metallic sodium, biphenyl and tetraethyleneglycol dimethyl ether (TEGDME) between metallic sodium and the space of electrolytic tube, the space between electrolytic tube and the battery container of cylindrical battery is equipped with the Na of 1 milliliter of 1mol/L2S8/ DMSO liquid positive electrode.Being placed in by battery in the baking oven of 70 DEG C and carry out constant current charge-discharge, voltage range is 1.8 to 2.5V electric currents is 5mA.Figure 11 is its second week charging and discharging curve, it can be seen that the discharge capacity of battery is 350mAh/g, and being charged to 2.5V capacity is that 350mAh/g has significantly high coulombic efficiency.Additionally the battery of the present invention is not limited at 70 DEG C to work, but includes from room temperature to the operation interval of 150 DEG C.
The metallic sodium of solid-state or lithium or potassium are placed in conductive liquid metal negative pole by the secondary cell that the embodiment of the present invention provides, and greatly improve the energy density of conductive liquid metal battery, have high safety and cheap cost.Can being applied to prepare the rich material resources of secondary cell of the present invention, the specific energy of battery is high, has extended cycle life, and can be used for the extensive energy storage device of solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
The parameters such as the temperature described in above-described embodiment, concentration, time; it is only specific embodiment; not limitation of the invention; those skilled in the art are not when paying creative work; all above-mentioned parameter can be adjusted; to obtain the effect identical with the present invention, therefore the adjustment of each parameter values all should be included in protection scope of the present invention.
Above-described detailed description of the invention; the purpose of the present invention, technical scheme and beneficial effect have been further described; it is it should be understood that; the foregoing is only the specific embodiment of the present invention; the protection domain being not intended to limit the present invention; all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (10)
1. a secondary cell, it is characterised in that described secondary cell includes the metallic sodium of solid-state or lithium or potassium, conductive liquid metal, solid electrolyte, positive electrode and battery container；
The metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal are placed in the solid electrolyte tube that described solid electrolyte is constituted, or, the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal are filled between described battery container and described solid electrolyte, and the metallic sodium of described solid-state or lithium or potassium constitute the negative pole of described secondary cell together with conductive liquid metal；
Described conductive liquid metal includes in metallic sodium, lithium, potassium any one or several and mixes the liquid generated with aromatic compound and ether solvent；
Described positive electrode is filled between described battery container and described solid electrolyte, forms the positive pole of described secondary cell；
Wherein, described positive electrode includes many sulphions solution, anthraquinone solution, benzoquinone solution, iodine solution, benzophenone solution, tetramethoxy piperidine oxide TEMPO solution, or Na0.44MnO2、NaTi2(PO4)3、Na3V2(PO4)3、Na0.8Li0.1Ni0.25Mn0.65O2、NaMg0.1Ni0.4Mn0.2Ti0.3O2, any one or more slurry constituted with carbon dust in S.
2. secondary cell according to claim 1, it is characterised in that described secondary cell is cylindrical battery；
Described solid electrolyte is tubulose, houses and in described battery container；
The metallic sodium of described solid-state or lithium or potassium are placed in described solid electrolyte tube, and conductive liquid metal is filled between metallic sodium or lithium or potassium and solid electrolyte.
3. secondary cell according to claim 1, it is characterised in that described secondary cell is double flow battery, and described battery also includes: positive pole fluid reservoir, negative pole fluid reservoir and two pumps；
Described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, wherein said positive pole space is connected with described positive pole fluid reservoir, is pumped in described positive pole space by described positive electrode accommodating in positive pole fluid reservoir by a pump；Described negative pole space is connected with described negative pole fluid reservoir, and in described negative pole fluid reservoir, the metallic sodium of accommodating solid-state or lithium or potassium and described conductive liquid metal, pumped into described conductive liquid metal accommodating in negative pole fluid reservoir in described negative pole space by a pump.
4. secondary cell according to claim 1, it is characterised in that described secondary cell is single flow battery, and described battery also includes: positive pole fluid reservoir and pump；
Described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, wherein said positive pole space is connected with described positive pole fluid reservoir, pumping in described positive pole space by described pump by described positive electrode accommodating in positive pole fluid reservoir, described negative pole space is used for housing the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal.
5. secondary cell according to claim 1, it is characterised in that described secondary cell is flat plate cell；
Described solid electrolyte is barrier film, described battery container is divided into airtight positive pole space and negative pole space, described positive pole space is used for housing described positive electrode, and described negative pole space is used for housing the metallic sodium of described solid-state or lithium or potassium and described conductive liquid metal material.
6. secondary cell according to claim 1, it is characterised in that
Described aromatic compound be in the derivant of biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene any one or multiple；
Described ether solvent include 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 any one or multiple.
7. secondary cell according to claim 1, it is characterised in that the preparation method of described conductive liquid metal includes:
In the protective atmosphere of argon, alkali metal and aromatic compound are added in ether solvent according to certain mol proportion, stands, obtain described conductive liquid metal negative material；
Wherein, described alkali metal be in metallic sodium, lithium metal or metallic potassium any one or multiple；
Described aromatic compound be in the derivant of biphenyl, connection benzene derivate, naphthalene, naphthalene derivatives, anthracene or anthracene any one or multiple；
Described ether solvent include 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 any one or multiple.
8. secondary cell according to claim 1, it is characterised in that described solid electrolyte includes the Na for conducts sodium ions, lithium ion or potassium ion3Zr2Si2PO12Pottery, Na-β "-Al2O3Pottery, K-β "-Al2O3Pottery, Li7La3Zr2O12Pottery or Li10GeP2S12Any one in pottery.
9. the purposes of the secondary cell as described in a claim as arbitrary in the claims 1-8, it is characterised in that described secondary cell is for the extensive energy storage device of solar electrical energy generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
10. the preparation method of the negative pole of the secondary cell as described in the claims 1, it is characterised in that described method includes:
In the protective atmosphere of argon, conductive liquid metal is injected in the solid electrolyte tube that solid electrolyte is constituted, or is injected between battery container and described solid electrolyte；
Excessive solid metallic sodium or lithium or potassium are inserted in conductive liquid metal；
Negative wire is drawn from solid metallic；
By after the sealing of the solid electrolyte mouth of pipe static two hours, namely obtain described negative pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410749445.XA CN105742727B (en) | 2014-12-09 | 2014-12-09 | A kind of preparation method of secondary cell, purposes and its cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410749445.XA CN105742727B (en) | 2014-12-09 | 2014-12-09 | A kind of preparation method of secondary cell, purposes and its cathode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105742727A true CN105742727A (en) | 2016-07-06 |
| CN105742727B CN105742727B (en) | 2018-05-22 |
Family
ID=56239559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410749445.XA Active CN105742727B (en) | 2014-12-09 | 2014-12-09 | A kind of preparation method of secondary cell, purposes and its cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105742727B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106182343A (en) * | 2016-08-17 | 2016-12-07 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery solid electrolyte ceramic pipe forming method |
| CN107565157A (en) * | 2017-07-26 | 2018-01-09 | 南京邮电大学 | A kind of porous nano crystalline substance sodium ion solid electrolyte and preparation method thereof |
| WO2018152754A1 (en) * | 2017-02-23 | 2018-08-30 | 深圳先进技术研究院 | Secondary battery and preparation method therefor |
| CN108470895A (en) * | 2018-03-21 | 2018-08-31 | 同济大学 | A kind of kalium ion battery positive electrode and preparation method thereof, potassium iodine battery |
| CN108649267A (en) * | 2018-05-11 | 2018-10-12 | 深圳市清新电源研究院 | A kind of potassium ion conductor and its preparation method and application |
| CN109378510A (en) * | 2018-10-25 | 2019-02-22 | 中盐金坛盐化有限责任公司 | The organic flow battery system of aqueous phase system based on salt cave |
| CN110380009A (en) * | 2019-07-03 | 2019-10-25 | 上海交通大学 | A kind of solid lithium battery cathode of lithium hot melt filling apparatus and method |
| CN111540937A (en) * | 2020-04-28 | 2020-08-14 | 天目湖先进储能技术研究院有限公司 | Large-capacity secondary battery and application thereof |
| CN112151770A (en) * | 2020-09-16 | 2020-12-29 | 天目湖先进储能技术研究院有限公司 | Preparation method of iron disulfide cathode material with pre-embedded lithium and lithium secondary battery |
| CN112751077A (en) * | 2019-10-30 | 2021-05-04 | 通用汽车环球科技运作有限责任公司 | Liquid metal interfacial layer for solid electrolyte and method therefor |
| CN112820935A (en) * | 2020-12-31 | 2021-05-18 | 长三角物理研究中心有限公司 | Novel battery based on sulfide solid electrolyte |
| CN113675376A (en) * | 2021-08-23 | 2021-11-19 | 哈尔滨工业大学 | Dendrite-free alkali metal ion battery based on solid/liquid phase conversion of negative electrode surface |
| WO2022222894A1 (en) * | 2021-04-19 | 2022-10-27 | 华为技术有限公司 | Metal negative electrode, battery, and electronic device |
| US11486046B2 (en) | 2020-03-04 | 2022-11-01 | Enlighten Innovations Inc. | Production of sodium metal by dual temperature electrolysis processes |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023515871A (en) * | 2020-03-04 | 2023-04-14 | フィールド アップグレイディング ユーエスエイ インコーポレイテッド | Rechargeable hybrid sodium metal-sulfur battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101018893A (en) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | Electrolysis cell for producing alkali metal |
| CN101136496A (en) * | 2006-08-31 | 2008-03-05 | 精工爱普生株式会社 | Secondary battery and a method for manufacturing the secondary battery |
| US20110136007A1 (en) * | 2009-12-07 | 2011-06-09 | Aruna Zhamu | Submicron-scale and lower-micron graphitic fibrils as an anode active material for a lithium ion battery |
| CN104078686A (en) * | 2013-03-26 | 2014-10-01 | Sk新技术株式会社 | Current collector for secondary battery and secondary battery comprising the same |
-
2014
- 2014-12-09 CN CN201410749445.XA patent/CN105742727B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101018893A (en) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | Electrolysis cell for producing alkali metal |
| CN101136496A (en) * | 2006-08-31 | 2008-03-05 | 精工爱普生株式会社 | Secondary battery and a method for manufacturing the secondary battery |
| US20110136007A1 (en) * | 2009-12-07 | 2011-06-09 | Aruna Zhamu | Submicron-scale and lower-micron graphitic fibrils as an anode active material for a lithium ion battery |
| CN104078686A (en) * | 2013-03-26 | 2014-10-01 | Sk新技术株式会社 | Current collector for secondary battery and secondary battery comprising the same |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106182343A (en) * | 2016-08-17 | 2016-12-07 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery solid electrolyte ceramic pipe forming method |
| CN106182343B (en) * | 2016-08-17 | 2018-11-27 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery solid electrolyte ceramic pipe forming method |
| WO2018152754A1 (en) * | 2017-02-23 | 2018-08-30 | 深圳先进技术研究院 | Secondary battery and preparation method therefor |
| CN107565157B (en) * | 2017-07-26 | 2020-05-05 | 南京邮电大学 | Microporous nanocrystalline sodium ion solid electrolyte and preparation method thereof |
| CN107565157A (en) * | 2017-07-26 | 2018-01-09 | 南京邮电大学 | A kind of porous nano crystalline substance sodium ion solid electrolyte and preparation method thereof |
| CN108470895A (en) * | 2018-03-21 | 2018-08-31 | 同济大学 | A kind of kalium ion battery positive electrode and preparation method thereof, potassium iodine battery |
| CN108649267A (en) * | 2018-05-11 | 2018-10-12 | 深圳市清新电源研究院 | A kind of potassium ion conductor and its preparation method and application |
| CN108649267B (en) * | 2018-05-11 | 2021-09-17 | 深圳市清新电源研究院 | Potassium ion conductor and preparation method and application thereof |
| CN109378510A (en) * | 2018-10-25 | 2019-02-22 | 中盐金坛盐化有限责任公司 | The organic flow battery system of aqueous phase system based on salt cave |
| CN110380009A (en) * | 2019-07-03 | 2019-10-25 | 上海交通大学 | A kind of solid lithium battery cathode of lithium hot melt filling apparatus and method |
| CN110380009B (en) * | 2019-07-03 | 2022-04-05 | 上海交通大学 | Lithium negative electrode hot melting filling device and method for all-solid-state lithium battery |
| CN112751077A (en) * | 2019-10-30 | 2021-05-04 | 通用汽车环球科技运作有限责任公司 | Liquid metal interfacial layer for solid electrolyte and method therefor |
| US11486046B2 (en) | 2020-03-04 | 2022-11-01 | Enlighten Innovations Inc. | Production of sodium metal by dual temperature electrolysis processes |
| CN111540937A (en) * | 2020-04-28 | 2020-08-14 | 天目湖先进储能技术研究院有限公司 | Large-capacity secondary battery and application thereof |
| CN111540937B (en) * | 2020-04-28 | 2022-01-25 | 天目湖先进储能技术研究院有限公司 | Large-capacity secondary battery and application thereof |
| CN112151770A (en) * | 2020-09-16 | 2020-12-29 | 天目湖先进储能技术研究院有限公司 | Preparation method of iron disulfide cathode material with pre-embedded lithium and lithium secondary battery |
| CN112820935A (en) * | 2020-12-31 | 2021-05-18 | 长三角物理研究中心有限公司 | Novel battery based on sulfide solid electrolyte |
| WO2022222894A1 (en) * | 2021-04-19 | 2022-10-27 | 华为技术有限公司 | Metal negative electrode, battery, and electronic device |
| CN113675376A (en) * | 2021-08-23 | 2021-11-19 | 哈尔滨工业大学 | Dendrite-free alkali metal ion battery based on solid/liquid phase conversion of negative electrode surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105742727B (en) | 2018-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742727B (en) | A kind of preparation method of secondary cell, purposes and its cathode | |
| CN105098140B (en) | Liquid metal negative material and room temperature liquid metal battery, preparation method and purposes | |
| CN102983316B (en) | Electrode material of a kind of secondary lithium battery and preparation method thereof | |
| CN106450247B (en) | Metal bismuth negative electrode and ether-based electrolyte for sodium/potassium ion secondary battery | |
| CN103219491B (en) | Copper sulfide anode and preparation method thereof | |
| CN104779394A (en) | Aqueous lithium (sodium) ion battery mixed negative material | |
| CN108232161A (en) | A kind of full battery of sodium ion | |
| CN104795567B (en) | Aquo-lithium ion/sodium-ion battery based on iodide ion solution anode and organic matter cathode | |
| CN103904356A (en) | Chargable chemical energy-storage device and application thereof | |
| CN104795564B (en) | A kind of positive electrode of Aqueous solution secondary battery, pole piece, secondary cell and purposes | |
| CN109301178A (en) | A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus | |
| CN105977526A (en) | Rechargeable aluminum carbon battery and preparation method thereof | |
| CN109546134A (en) | The negative electrode material and sodium-ion battery a kind of sodium-ion battery cathode pre- sodium modification method and obtained | |
| CN104701541A (en) | Lithium-ion battery with WS2 serving as positive electrode and preparation method of lithium-ion battery | |
| CN101262056A (en) | A water solution chargeable lithium ion battery | |
| CN104183832A (en) | Preparation method and application of FeF3 flexible electrode based on carbon nano tube-graphene composite three-dimensional network | |
| CN102263280A (en) | Flow aqueous chargeable alkali metal ion battery | |
| CN109301247A (en) | A kind of novel organic potassium ion battery cathode material, synthetic method and application | |
| CN105742695A (en) | Lithium-ion battery and preparation method thereof | |
| Hu et al. | In-situ construction of dual lithium-ion migration channels in polymer electrolytes for lithium metal batteries | |
| CN107706446A (en) | A kind of all solid lithium carbon dioxide secondary cell | |
| CN110085864A (en) | The preparation method and application of potassium or based lithium-ion battery positive plate | |
| CN104300175B (en) | A kind of room temperature sodium-sulfur secondary battery | |
| CN105428704A (en) | Modified oxidation-reduction type solid electrolyte as well as preparation method and application thereof | |
| CN112768766A (en) | Lithium-sulfur battery electrolyte and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |