CN105048004A - Thermally activated secondary battery using low-temperature molten salt electrolyte - Google Patents
Thermally activated secondary battery using low-temperature molten salt electrolyte Download PDFInfo
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- CN105048004A CN105048004A CN201510341748.2A CN201510341748A CN105048004A CN 105048004 A CN105048004 A CN 105048004A CN 201510341748 A CN201510341748 A CN 201510341748A CN 105048004 A CN105048004 A CN 105048004A
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- lithium
- molten salt
- temperature molten
- secondary cell
- oxygen
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
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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
- 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 provides a thermally activated secondary battery using a low-temperature molten salt electrolyte based on a lithium/oxygen reaction mechanism. The thermally activated secondary battery comprises the low-temperature molten salt electrolyte, a lithium cathode, an oxygen anode and a diaphragm positioned between the anode and the cathode, wherein the low-temperature molten salt electrolyte consists of alkali metal cations and di(sulfonyl fluoride)imine anions, and particularly consists of di(sulfonyl fluoride)lithium imide and one, two or three of four non-lithium salts, namely, di(sulfonyl fluoride)sodium imide, di(sulfonyl fluoride)potassium imide, di(sulfonyl fluoride)rubidium imide and di(sulfonyl fluoride)cesium imide. The molten salt electrolyte in the invention is in a molten state at the temperature of 40-100 DEG C, and has the advantages of low melting temperature, freeness from volatilization, incombustibility, high chemical stability and high ion conductivity. Charging and discharging reactions are finished on the basis of a lithium/oxygen reaction, so that the problems of high battery working temperature, short working time after activation, low energy density, failure in charging after activation and the like in a conventional thermally activated battery can be effectively solved. The thermally activated secondary battery provided by the invention has wide application prospects in the fields of national defense, industrial use and civil use.
Description
Technical field
The present invention relates to a kind of electrochemical energy storing device, particularly one uses the electrolytical hot activation secondary cell of low temperature molten salt.
Background technology
Thermal cell is a kind of heat activated reserve cell, and it uses the heating system of battery self nonconducting solid-state salt electrolyte heating and melting is become ionic conductor and enters operating state.Thermal cell, once be activated, as long as electrolyte keeps molten condition, just constantly can export electric energy, until the active material participating in reaction exhausts, or battery also can be caused to stop output electric energy because inside battery heat lost makes electrolyte again solidify.Thermal cell because having high power discharge, high-specific-power, environment for use temperature are wide, the storage time long, activate the feature such as reliable, compact conformation rapidly, in military, industry and civil area, occupy very consequence.
Single cell of thermo is all made up of alkali metal or alkaline-earth metal negative pole, molten salt electrolyte and slaine positive pole usually.Fireworks heating material is inserted in the middle of each cell of series connection pile usually.In thermal cell, anode not only participates in electrochemical reaction, but also plays electric action.The metal material that the anode material of thermal cell generally adopts electrode potential comparatively to bear, as calcium, magnesium, lithium etc.At present, adopt the thermal cell of lithium anode increasing, because lithium anode can avoid some shortcomings of calcium anode.But lithium is directly as the anode of thermal cell, its fusing point lower (180 DEG C), is in a liquid state, easily overflows from porous current collector under the working temperature of thermal cell, usually needs to carry out anti-spilled design to lithium and causes battery short circuit to avoid spilling.In lithium system thermal cell, excellent cathode active material generally needs to have following characteristics: electrode potential is high, relative to lithium current potential more preferably greater than 3V; There is high thermal stability; Do not react with electrolyte; There is electron conduction, can heavy-current discharge; The product generated can be conducted electricity and maybe can be dissolved in electrolyte, reduces internal resistance.The cathode material of lithium system thermal cell, adopts the metal sulfide of current potential calibration, oxide and chloride usually.Transition-metal sulphides is the good thermal cell cathode material of a class, replaces sulphur and does cathode material, can solve the loss problem of sulphur steam under high temperature, greatly reduce the formation dissolving in electrolytical polysulfide with its.FeS
2it is the most widely used thermal cell cathode material mated with lithium anode at present.
The molten salt electrolyte of thermal cell has the incomparable superiority of aqueous electrolyte: illiquidity, high conductivity and Ion transfer speed are large, permission high-power high-current is discharged, decomposition voltage is high, ultralow noble potential metal and alloy thereof can be used to make anode; Thus make that cell output voltage is high, specific energy is large, active material utilization is high, electrochemical polarization and concentration polarization all very little.Conventional thermoelectric pond electrolyte selects the fluoride of alkali and alkaline earth metal ions, chloride, bromide and their eutectic point mixture.But these electrolytical fusing points are relatively high, the working temperature of battery is substantially all at 300 ~ 500 DEG C.In recent years, abroad some thermal cell laboratories adopt the nitrate of melting to be applied to lithium system thermal battery electrolyte.Adopt molten nitrate as lithium system thermal battery electrolyte, battery operating temperature scope low (150 ~ 300 DEG C), and have good conductance, this system is applied in thermal cell, and system temperature more traditional lithium system thermal cell reduces at least 100 DEG C; Lithium system anode can be compatible with it; Adopt high voltage negative electrode and lithium anode to match, the monomer voltage of battery and specific energy comparatively Conventional thermoelectric pond can be significantly improved.
At present, thermal cell has been widely used in the field such as national defence and military affairs, but thermal cell still faces following shortcoming: the operating time shorter (being usually no more than 10min) after 1) activating; 2) medium specific energy on the low side, energy density is no more than 40Wh/kg usually; 3) battery operating temperature high (generally all at the fusing point of lithium that is on 180 DEG C); 4) can only single use after activating, cannot charge.Therefore, exploitation has the hot activation secondary cell of long operating time and high-energy-density, low working temperature (lower than the fusing point of lithium, namely 180 DEG C), is significant and is rich in challenge.
In recent years, the lithium/oxygen reaction in nonaqueous phase is extensively concerned, ideally, can be represented in non-aqueous solution electrolysis plastidome lithium/oxygen reaction process by formula (1).Particularly, Li
+and O
2reaction forms Li
2o
2; And Li
2o
2oxidation Decomposition produces Li and O
2, this reaction can reversibly be carried out.
2Li
++O
2+2e
-←→Li
2O
2(E
0=2.96VvsLi/Li
+)(1)
If follow above-mentioned lithium/oxygen reaction mechanism construction energy-storage battery, then there is high theoretical specific energy, even if cathode of lithium, air electrode and electrolyte are all included, the specific energy density of lithium-aeration cell is still up to 2790Wh/kg, the 5-10 being lithium-ion battery system doubly, is 10-30 times of Conventional thermoelectric pond.If above-mentioned lithium/oxygen reaction is incorporated in thermally activated battery system, is then expected to the energy density significantly promoting battery, and hot activation secondary cell can be built into.
But the intermediate product that above-mentioned (1) reaction generates is strong nucleopilic reagent, can react with the organic electrolyte such as at present conventional most of carbonates, ethers and organic ion liquid type, cause generating the accessory substances such as lithium carbonate, lithium hydroxide, alkyl lithium carbonates, carbon dioxide and water, greatly will affect the performance of battery, result in the problems such as discharge and recharge polarization is large, coulombic efficiency is low, cycle performance is poor.Adopt have non-volatile, non-combustible, fail safe is good, chemical stability and electrochemical stability is high, the molten salt electrolyte of ionic conductivity advantages of higher, is expected to solve the bottleneck problem that conventional organic electrolyte system faces.Be widely used in the electrolyte system melt temperatures such as the fused chloride of thermal cell, molten nitrate at present generally higher, need a lot of external energy supplies that battery could be kept in running order, reduce energy utilization efficiency and add danger.Two (fluorine sulphonyl) imido grpup alkali metal salt (alkalibis (fluorosulfonyl) imides, MFSI (M=Li, Na, K, Rb, Cs)) generally there is lower fusing point, and the mixture of the binary that phasor displaying ratio is determined or ternary has single fusion point, and its eutectic melt temperature is greatly reduced, phase transition temperature is positioned at 40 DEG C of-100 DEG C of intervals, if LiFSI-KFSI(molar percentage is 41-59) melt temperature be 74 DEG C, LiFSI-KFSI-CsFSI(molar percentage is 30-35-35) melt temperature be only 39 DEG C of (J.Chem.Eng.Data, 2010, 55, 3142-3146, Electrochim.Acta, 2012,66,320-324).After the melting of two (fluorine sulphonyl) imido grpup alkali metal salt, there is good conductivity.
Summary of the invention
The present invention, in order to solve the above-mentioned Problems existing of conventional thermally activated battery, provides and a kind of uses two (fluorine sulphonyl) imido grpup alkali metal alkali low temperature molten salt electrolyte, discharge and recharge based on the hot activation secondary cell of lithium/oxygen reaction.
To achieve these goals, technical scheme of the present invention is:
The electrolytical hot activation secondary cell of a kind of use low temperature molten salt, comprise watery fusion salt electrolyte, cathode of lithium, oxygen positive pole and the barrier film between both positive and negative polarity, described watery fusion salt electrolyte is made up of jointly two (fluorine sulphonyl) imine lithium and the one, two or three in two (fluorine sulphonyl) imines sodium, two (fluorine sulphonyl) imines potassium, two (fluorine sulphonyl) imines rubidium, two (fluorine sulphonyl) imines caesium four kinds of non-lithium salts.
Described hot activation secondary cell, its exoelectrical reaction generates lithium peroxide based on lithium/oxygen reaction and completes, and charging reaction decomposes generation lithium based on lithium peroxide and oxygen completes.
Described hot activation secondary cell, its working temperature interval is 40 DEG C to 180 DEG C, is no more than the fusing point of lithium anode.
Described hot activation secondary cell, lithium titanate cathode material is the one of metal Li, LiSi alloy, LiAl alloy.
Described hot activation secondary cell, oxygen just very loose structure, be made up of electric conducting material.One in the material with carbon elements such as the preferred conductive black of electric conducting material, carbon nano-tube, Graphene, mesoporous carbon, or the one in the metal material such as gold, platinum, palladium, or transition metal oxide, one in transition metal nitride, or the mixture of above-mentioned material.
Described hot activation secondary cell, the barrier film between both positive and negative polarity is the one in glass fibre membrane, lithium ion permeability ceramic membrane, cellulose base barrier film, and the penetrating ceramic membrane of lithium ion is LISICON structure, LiLaTiO
3one in perovskite structure ceramic membrane.
the advantage that the present invention has and good effect:
Compared with existing thermally activated battery, the present invention with the low temperature molten salt be made up of alkali metal cation and two (fluorine sulphonyl) imines anion for electrolyte, phase transition temperature is positioned at 40 DEG C of-100 DEG C of intervals, compares other fuse salt systems and has the advantages such as melt temperature is low, good stability.Battery operating temperature is not higher than 180 DEG C, even if be negative pole with lithium metal, it still keeps solid-state, without the need to additionally carrying out anti-spilled design to lithium, improves battery security.Hot activation secondary cell provided by the present invention generates lithium peroxide with lithium/oxygen reaction and is discharge process, decomposes generate lithium and oxygen for charging reaction with lithium peroxide, have that energy density is high, discharge voltage is high, activate after longevity of service, activate after can the advantage such as recharging.Hot activation secondary cell provided by the present invention adopts double starting to arrange, and namely warm start and oxygen input, have better fail safe and controllability.Hot activation secondary cell provided by the present invention has good application prospect in the field such as new forms of energy and national defence.
Accompanying drawing explanation
The differential scanning calorimetric curve of the watery fusion salt electrolyte (LiFSI:NaFSI:KFSI=0.3:0.4:0.3, mol ratio) used in Fig. 1 embodiment of the present invention 1.
The structural representation of the electrolytical hot activation secondary cell of low temperature molten salt is used in Fig. 2 the present invention.
The use low temperature molten salt that Fig. 3 embodiment of the present invention 1 provides is electrolytical, based on the charging and discharging curve of the hot activation secondary cell of lithium/oxygen reaction.
Embodiment
The present invention in order to the battery operating temperature solving existing electrochemical energy storage thermally activated battery and face is high, activate after the operating time short and energy density is low, activate after the problem such as can not to charge, provide and a kind ofly use the watery fusion salt electrolyte of alkali metal cation and two (fluorine sulphonyl) imines anion composition, carry out the hot activation secondary cell of discharge and recharge based on lithium/oxygen reaction.Compared to conventional thermally activated battery, the working temperature reducing battery, the operating time that improve battery and energy density, fail safe by adopting thermal excitation and oxygen input double starting to improve battery.
embodiment 1
the determination of watery fusion salt electrolyte phase transition temperature: be full of in argon gas glove box, taking a certain amount of LiFSI, NaFSI and KFSI respectively according to the molar ratio of 3:4:3, evenly, said mixture is carried out means of differential scanning calorimetry test, and curve obtained is as Fig. 1 in grinding, can find that this fuse salt system has the phase transition temperature determined, be 45 DEG C.
use the assembling of the electrolytical hot activation secondary cell of low temperature molten salt: the structure of the hot activation secondary cell assembled is as shown in Figure 2.Take diameter as 1.2cm, thickness be the metal lithium sheet of 200 μm is battery cathode.By material with carbon element SuperP and polyfluortetraethylene of binding element (PTFE) in mass ratio 90:10 ratio mixing, stir form slurry, evenly applied by this slurry and to be compacted at stainless steel collector online, is cut into the anode pole piece of diameter 1.2cm.Using above-mentioned positive and negative pole material, measure about 300 μ LLiFSI-NaFSI-KFSI(0.3:0.4:0.3) molten mass is electrolyte, Whatman glass fibre membrane is that barrier film assembled heat activates secondary cell.
use the test of the electrolytical hot activation secondary cell of low temperature molten salt: positive pole, negative pole are formed loop, adopts the current density of 50mA/g (supreP), oxygen pressure 1atm, battery temperature to be 50 DEG C and to carry out charge-discharge test.Accompanying drawing 3 is its charging and discharging curve, this hot activation secondary cell under this electric current, very little electric discharge polarization under (about 0.1V), the specific discharge capacity based on superP material with carbon element quality can reach 1300mAh/g; This hot activation secondary cell under this electric current, very little charging polarization (<0.2V) under, the charge specific capacity based on superP material with carbon element quality can reach more than 1200mAh/g.
embodiment 2
The watery fusion salt electrolyte adopted in embodiment 1 is changed into the LiFSI-KFSI of mol ratio 0.41:0.59, the manufacturing process of all the other hot activation secondary cells is identical with embodiment 1.
use the test of the electrolytical hot activation secondary cell of low temperature molten salt: through means of differential scanning calorimetry test, the melt temperature of the LiFSI-KFSI molten salt electrolyte of mol ratio 0.41:0.59 is 68 DEG C.The electrolytical hot activation anode of secondary battery of low temperature molten salt, negative pole will be used to form loop, adopt the current density of 50mA/g (supreP), oxygen pressure 1atm, battery temperature to be 70 DEG C and to carry out charge-discharge test.Hot activation secondary cell is under this electric current, under less electric discharge and charging polarization (being not more than 0.2V), can reach about 1200mAh/g based on the electric discharge of superP material with carbon element quality and charge specific capacity, and have good capability retention.
Claims (6)
1. one kind uses the electrolytical hot activation secondary cell of low temperature molten salt, comprise watery fusion salt electrolyte, lithium an-ode, oxygen positive pole and the barrier film between both positive and negative polarity, described watery fusion salt electrolyte is made up of jointly two (fluorine sulphonyl) imine lithium and the one, two or three in two (fluorine sulphonyl) imines sodium, two (fluorine sulphonyl) imines potassium, two (fluorine sulphonyl) imines rubidium, two (fluorine sulphonyl) imines caesium four kinds of non-lithium salts.
2. one according to claim 1 uses the electrolytical hot activation secondary cell of low temperature molten salt, it is characterized in that: based on lithium/oxygen reaction mechanism, the exoelectrical reaction of battery generates lithium peroxide based on lithium/oxygen reaction and completes, and charging reaction decomposes generation lithium based on lithium peroxide and oxygen completes.
3. one according to claim 1 uses the electrolytical hot activation secondary cell of low temperature molten salt, it is characterized in that: battery operating temperature interval is 40 DEG C to 180 DEG C.
4. one according to claim 1 uses the electrolytical hot activation secondary cell of low temperature molten salt, it is characterized in that: cathode of lithium is the one of metal Li, LiSi alloy, LiAl alloy.
5. one according to claim 1 uses the electrolytical hot activation secondary cell of low temperature molten salt, it is characterized in that: oxygen is loose structure just very, is made up of electric conducting material.
6. one according to claim 1 uses the electrolytical hot activation secondary cell of low temperature molten salt, it is characterized in that: the barrier film between both positive and negative polarity is the one in glass fibre membrane, lithium ion permeability solid-state ceramic film, cellulose base barrier film.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110120495A (en) * | 2019-04-12 | 2019-08-13 | 贵州梅岭电源有限公司 | A kind of composite positive pole and preparation method and application reducing self discharge degree |
| CN112952125A (en) * | 2021-03-02 | 2021-06-11 | 厦门大学 | Electrolyte structure of thermal activation battery and application thereof |
| CN112952126A (en) * | 2021-03-02 | 2021-06-11 | 厦门大学 | Thermally activated battery structure and application thereof |
| CN114843704A (en) * | 2022-04-20 | 2022-08-02 | 天津大学 | Manganese-containing fluoride thermal battery |
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| WO2014153551A1 (en) * | 2013-03-21 | 2014-09-25 | Liox Power, Inc. | Alkali metal/oxygen batteries employing molten nitrate electrolytes |
-
2015
- 2015-06-18 CN CN201510341748.2A patent/CN105048004A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014153551A1 (en) * | 2013-03-21 | 2014-09-25 | Liox Power, Inc. | Alkali metal/oxygen batteries employing molten nitrate electrolytes |
Non-Patent Citations (1)
| Title |
|---|
| KEIGO KUBOTA 等: "《New inorganic ionic liquids possessing low melting temperatures and wide electrochemical windows: Ternary mixtures of alkali bis(fluorosulfonyl)amides》", 《ELECTROCHIMICA ACTA》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110120495A (en) * | 2019-04-12 | 2019-08-13 | 贵州梅岭电源有限公司 | A kind of composite positive pole and preparation method and application reducing self discharge degree |
| CN112952125A (en) * | 2021-03-02 | 2021-06-11 | 厦门大学 | Electrolyte structure of thermal activation battery and application thereof |
| CN112952126A (en) * | 2021-03-02 | 2021-06-11 | 厦门大学 | Thermally activated battery structure and application thereof |
| CN114843704A (en) * | 2022-04-20 | 2022-08-02 | 天津大学 | Manganese-containing fluoride thermal battery |
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