CN103579719A - Electrolyte for lithium air battery and lithium air battery composed thereof - Google Patents

Electrolyte for lithium air battery and lithium air battery composed thereof Download PDF

Info

Publication number
CN103579719A
CN103579719A CN201210270494.6A CN201210270494A CN103579719A CN 103579719 A CN103579719 A CN 103579719A CN 201210270494 A CN201210270494 A CN 201210270494A CN 103579719 A CN103579719 A CN 103579719A
Authority
CN
China
Prior art keywords
lithium
electrolyte
battery
air
air electrode
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.)
Pending
Application number
CN201210270494.6A
Other languages
Chinese (zh)
Inventor
谢晓华
康亚楠
娄豫皖
张建
夏保佳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Microsystem and Information Technology of CAS
Original Assignee
Shanghai Institute of Microsystem and Information Technology of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Microsystem and Information Technology of CAS filed Critical Shanghai Institute of Microsystem and Information Technology of CAS
Priority to CN201210270494.6A priority Critical patent/CN103579719A/en
Publication of CN103579719A publication Critical patent/CN103579719A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention relates to an electrolyte for a lithium air battery and a lithium air battery composed of the electrolyte. The electrolyte consists of lithium salt and an organic solvent with high boiling point and low volatility. The lithium air battery consists of a button battery shell, a lithium anode, a diaphragm, an electrolyte, a protective air electrode and a sealing ring, wherein one or more vent holes are formed in an anode shell of the button battery to provide oxygen for an electrochemical reaction; the protective air electrode consists of an air electrode and a protective film; the protective film can inhibit the invasion of moisture in the air and can prevent the volatilization of the electrolyte in the battery; the air tightness of the battery is realized by the sealing ring. The button lithium air battery provided by the invention has strong environmental suitability and is suitable for application occasions with small current and needing long-time work.

Description

The lithium-air battery of electrolyte and formation thereof for a kind of lithium-air battery
Technical field
The present invention relates to a kind of lithium metal air cell, particularly disclose a kind of lithium-air battery with electrolyte and comprise the lithium-air battery that this electrolyte forms, belong to chemical power source and association area.
Background technology
Lithium-air battery is a kind of novel chemical energy storage battery, it combines the advantage separately of lithium ion battery and fuel cell: adopting the lithium metal that electrochemical equivalent is the highest and the air not being stored in battery system is active material, its theoretical specific energy surpasses 10,000 Wh/kg(reality and only reaches 600-800Wh/g), far exceed Ni-MH battery and lithium ion battery, be expected to break through the technical bottleneck that current chemical cell energy density cannot further significantly improve, application prospect is very wide.
Because lithium-air battery is worked under open environment, common organic electrolyte has effumability, can accelerate the discharge off of battery, and while lithium salts is easily moisture absorption decomposition also, thereby has affected discharge capacity, useful life and the fail safe of battery.For this reason, the button lithium-air battery that present inventor attempts to provide a kind of electrolyte and is comprised of this electrolyte, to overcome the defect existing.
Summary of the invention
The present invention seeks to overcome a prior art difficult problem, provide a kind of lithium-air battery with electrolyte and comprise the lithium-air battery that this electrolyte forms.This electrolyte is comprised of the organic solvent of lithium salts and higher boiling point, low volatility.This battery is by button cell shell, and lithium anode, barrier film, electrolyte, protective air electrode, sealing ring form.Wherein on the anode cover of button cell, open one or more a plurality of air vent holes, according to discharge current density size, provide electrochemical reaction needed oxygen; Through-hole diameter is 0.5-15mm, is generally 1-3mm and is advisable, and too large or too little being all difficult to meets the demands.Protective air electrode is comprised of air electrode and oxygen selective protecting film, suppresses the intrusion of moisture in air and the volatilization of inside battery electrolyte; The sealing of battery is realized by sealing ring.The button lithium-air battery environmental suitability of making is thus strong, the application scenario that be applicable to little electric current, works long hours.
Technical scheme of the present invention is: electrolyte provided by the invention comprises lithium salts and organic solvent, and wherein lithium salts is hexafluoroarsenate lithium (LiAsF 6), lithium hexafluoro phosphate (LiPF 6), lithium perchlorate (LiClO 4), one or more in two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) etc. mix, concentration is 0.1 ~ 3.0M, is preferably the LiAsF not reacting with water 6, LiClO 4with the one or more combination in LiTFSI, concentration is preferably 0.7 ~ 1.5M; Organic solvent is one or more the mixing in propylene carbonate ester (PC), ethylene carbonate (EC), butylene (BC), gamma-butyrolacton (GBL), methyl-sulfoxide (DMSO), DMF (DMF), sulfolane (SL), dimethyl sulfone (MSM) etc.Button cell shell can be selected a kind of as in CR1130, CR1220, CR1616, CR1620, CR2016, CR2025, CR2032, CR2330, CR2430, CR2450, CR2477 etc. of current version, according to the size of discharge current density, on anode cover, open one or more air vent holes, to provide electrochemical reaction needed oxygen.Lithium anode provides electrochemical reaction needed lithium, and one or more in lithium metal, lithium silicon alloy, lithium boron alloy, lithium-aluminium alloy etc. form.Barrier film is existing lithium ion battery barrier film, as PP, PE, PP/PE/PP film.Protective air electrode is comprised of air electrode and waterproof ventilated membrane, and air electrode is made after slurry by a certain percentage by material with carbon element, binding agent and catalyst, and it is evenly coated in nickel foam, through roll-in, makes air electrode; Material with carbon element is one or more in acetylene black, superconduction carbon black, Graphene, BP2000 and KB etc.; Binding agent is a kind of in polytetrafluoroethylene (PTFE), Kynoar (PVDF) etc.; Catalyst can be Pt, Pt-Au, Pd, PdCo, MnO 2, Co 3o 4, Fe 3o 4, MnOOH, Mn 3o 4and Fe 2o 3in one or more; One or more in polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), dimethyl silicone polymer (PDMS), PETG (PET) etc. of ventilated membrane form.Lithium anode, barrier film, protective air electrode, sealing ring are overlayed in negative battery shell successively, then cover positive battery shell, after sealing, make the empty battery of the button lithium that can work of the present invention in air.
The empty battery of button lithium provided by the invention, owing to having adopted the electrolyte of low volatility and the air electrode of protective, can suppress entering of moisture in air, can suppress again the volatilization of inside battery electrolyte, good environmental adaptability, suitable little electric current, the application scenario working long hours.
Accompanying drawing explanation
Discharge curve in the climatic chamber that Fig. 1 lithium-air battery is 30% 25 ℃ of relative humidity
Embodiment
Specific embodiments of the invention are as follows, but the present invention is not limited to following examples.
Comparative example 1
The making of air electrode: material with carbon element (Ketjen black ECP600JD) is mixed with appropriate ultra-pure water, stir after 30min, add PTFE emulsion, continue to stir 1h, the mass ratio of material with carbon element and PTFE is 85:15, then it is evenly coated in nickel foam, through roll-in, makes air electrode.
The making of button cell: in glove box, air electrode is immersed in to 1M LiPF 6in EC:DEC:EMC (1:1:1, vol%), after air electrode is all wetting, take out, with paper handkerchief, surface electrolyte is cleaned; Lithium metal, PP/PE/PP barrier film, air electrode, PDMS, PE, sealing ring are overlayed in negative battery shell successively, then cover positive battery shell (air vent hole diameter is 2mm), after sealing, take out, obtain the empty battery of lithium.
Comparative example 2
The air electrode that adopts comparative example 1 to make is made the empty battery of button lithium.The manufacture method of button cell is identical with comparative example 1, and different is that electrolyte is 1M LiClO 4eC:PC:DEC (4:4:2, vol%), obtains the empty battery of lithium.
Embodiment 1
The air electrode that adopts comparative example 1 to make is made the empty battery of button lithium.The manufacture method of button cell is identical with comparative example 1, and different is that electrolyte is 1M LiPF 6eC:PC (1:1, vol%), obtains the empty battery of lithium.
Embodiment 2
The air electrode that adopts comparative example 1 to make is made the empty battery of button lithium.The manufacture method of button cell is identical with comparative example 1, and different is that electrolyte is 1M LiClO 4eC:PC (1:1, vol%), obtains the empty battery of lithium.
Embodiment 3
The air electrode that adopts comparative example 1 to make is made the empty battery of button lithium.The manufacture method of button cell is identical with comparative example 1, and different is that electrolyte is 1M LiAsF 6eC:PC (1:1, vol%), obtains the empty battery of lithium.
The empty battery of lithium that comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3 are made, discharges in the climatic chamber that to be placed on 25 ℃, relative humidity be 30%, and current density is 0.1mA/cm 2, cut-ff voltage is 1.5V, result is as shown in Figure 1.Because the volatility of electrolyte itself reduces, add PDMS and PE and can suppress preferably moisture and enter and prevent electrolyte volatilization, make to compare with comparative example embodiment 1 ~ 3(curve 3,4 and 5) the empty battery discharge time of lithium obviously extend.
Above specific embodiment is only part execution mode of the present invention, and it is illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art, in the situation that not exceeding spirit and scope of the invention, converts, revises even equivalence to it, and these changes all can fall into claim protection range of the present invention.

Claims (8)

1. the electrolyte that lithium-air battery is used, is characterized in that described electrolyte is comprised of the organic solvent of lithium salts and higher boiling point, low volatility, and described lithium salts is hexafluoroarsenate lithium LiAsF 6, lithium hexafluoro phosphate LiPF 6, lithium perchlorate LiClO 4with one or more mixing in two (trifluoromethane sulfonic acid) imine lithium LiTFSI; Described organic solvent is one or more the mixing in propylene carbonate ester PC, ethylene carbonate EC, butylene BC, gamma-butyrolacton GBL, methyl-sulfoxide DMSO, DMF DMF, sulfolane SL and dimethyl sulfone MSM; In the electrolyte forming, lithium salt is 0.1 ~ 3.0M.
2. by electrolyte claimed in claim 1, it is characterized in that described lithium salts is LiAsF 6, LiPF 6, LiClO 4with one or more mixing in LiTFSI.
3. by electrolyte claimed in claim 1, it is characterized in that formed electrolyte lithium salt is 0.7-1.5M.
4. the lithium-air battery that the electrolyte described in any one forms in claim 1-3, the lithium-air battery described in it is characterized in that comprises by button cell shell, lithium anode, barrier film, electrolyte, protective air electrode and sealing ring and forming;
Wherein, 1. on the anode cover of button cell shell, open one or more a plurality of air vent holes, provide electrochemical reaction required oxygen;
2. protective air electrode is comprised of air electrode and waterproof ventilated membrane;
3. lithium anode, barrier film, protective air electrode, sealing ring overlay in negative battery shell successively, then cover the button lithium-air battery that obtains working in air after the sealing of positive battery shell.
5. by lithium-air battery claimed in claim 4, it is characterized in that the positive pole of described button cell, the through-hole diameter on housing is according to discharge current density size, and the diameter of through hole is 0.5-15mm.
6. by the lithium-air battery described in claim 4 or 5, it is characterized in that described through-hole diameter is 1-3mm.
7. by lithium-air battery claimed in claim 4, it is characterized in that:
(a) to select model be any in CR1130, CR1220, CR1616, CR1620, CR2016, CR2025, CR2032, CR2330, CR2430, CR2450 and CR2477 to button cell shell;
(b) the needed lithium of electrochemical reaction is provided is one or more formations in lithium metal, lithium silicon alloy, lithium boron alloy, lithium-aluminium alloy to lithium anode;
(c) barrier film is PP, PE or PP/PE/PP film lithium ion battery barrier film;
(d) protective air electrode is comprised of air electrode and waterproof ventilated membrane, and air electrode is made after slurry by material with carbon element, binding agent and catalyst by proportion, and it is evenly coated in nickel foam, through roll-in, makes air electrode; Material with carbon element is one or more in acetylene black, superconduction carbon black, Graphene, BP2000 and KB etc.; Binding agent is polytetrafluoroethylene PTFE or Kynoar PVDF; Catalyst is Pt, Pt-Au, Pd, PdCo, MnO 2, Co 3o 4, Fe 3o 4, MnOOH, Mn 3o 4and Fe 2o 3in one or more; One or more in polytetrafluoroethylene PTFE, polythene PE, polypropylene PP, polydimethylsiloxane and PETG of ventilated membrane form.
8. by the lithium-air battery described in claim 4 or 7, it is characterized in that described ventilated membrane is the bilayer of PDMS one deck or PDMS and PE composition.
CN201210270494.6A 2012-07-31 2012-07-31 Electrolyte for lithium air battery and lithium air battery composed thereof Pending CN103579719A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210270494.6A CN103579719A (en) 2012-07-31 2012-07-31 Electrolyte for lithium air battery and lithium air battery composed thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210270494.6A CN103579719A (en) 2012-07-31 2012-07-31 Electrolyte for lithium air battery and lithium air battery composed thereof

Publications (1)

Publication Number Publication Date
CN103579719A true CN103579719A (en) 2014-02-12

Family

ID=50051005

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210270494.6A Pending CN103579719A (en) 2012-07-31 2012-07-31 Electrolyte for lithium air battery and lithium air battery composed thereof

Country Status (1)

Country Link
CN (1) CN103579719A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105186069A (en) * 2015-09-24 2015-12-23 江苏帕维电动科技有限公司 Ether electrolyte applied to lithium-air battery and lithium-air battery
TWI571303B (en) * 2015-12-03 2017-02-21 財團法人金屬工業研究發展中心 Lithium boron alloy heat release control device and method
CN107275721A (en) * 2017-06-21 2017-10-20 昆明理工大学 A kind of organic/water mixed stocker sodium air cell based on acidic electrolysis bath
CN107317060A (en) * 2017-05-11 2017-11-03 中国科学院合肥物质科学研究院 A kind of charging method of metal-air battery and the battery using the charging method
CN108183241A (en) * 2017-12-29 2018-06-19 张树雄 A kind of air electrode and its catalysis slurry preparation method
CN115036520A (en) * 2022-05-30 2022-09-09 长虹三杰新能源有限公司 Aqueous lithium-air battery composite oxygen electrode catalyst and preparation method of composite oxygen electrode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101267057A (en) * 2008-05-08 2008-09-17 复旦大学 High ratio energy chargeable full-solid lithium air battery
CN101683613A (en) * 2008-09-22 2010-03-31 北京长力联合能源技术有限公司 Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101267057A (en) * 2008-05-08 2008-09-17 复旦大学 High ratio energy chargeable full-solid lithium air battery
CN101683613A (en) * 2008-09-22 2010-03-31 北京长力联合能源技术有限公司 Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
WU XU, ET AL: ""Effects of Nonaqueous Electrolytes on the Performance of Lithium/Air Batteries"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *
WU XU, ET AL: ""Optimization of Nonaqueous Electrolytes for Primary Lithium/Air Batteries Operated in Ambient Environment"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *
康亚楠，等: ""电解液组成对锂空气电池放电性能的影响"", 《第29届全国化学与物理电源学术年会论文集》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105186069A (en) * 2015-09-24 2015-12-23 江苏帕维电动科技有限公司 Ether electrolyte applied to lithium-air battery and lithium-air battery
TWI571303B (en) * 2015-12-03 2017-02-21 財團法人金屬工業研究發展中心 Lithium boron alloy heat release control device and method
CN107036297A (en) * 2015-12-03 2017-08-11 财团法人金属工业研究发展中心 Heat release control device and method for lithium boron alloy
CN107317060A (en) * 2017-05-11 2017-11-03 中国科学院合肥物质科学研究院 A kind of charging method of metal-air battery and the battery using the charging method
CN107275721A (en) * 2017-06-21 2017-10-20 昆明理工大学 A kind of organic/water mixed stocker sodium air cell based on acidic electrolysis bath
CN108183241A (en) * 2017-12-29 2018-06-19 张树雄 A kind of air electrode and its catalysis slurry preparation method
CN115036520A (en) * 2022-05-30 2022-09-09 长虹三杰新能源有限公司 Aqueous lithium-air battery composite oxygen electrode catalyst and preparation method of composite oxygen electrode
CN115036520B (en) * 2022-05-30 2023-06-30 长虹三杰新能源有限公司 Composite oxygen electrode catalyst of water system lithium air battery and preparation method of composite oxygen electrode

Similar Documents

Publication Publication Date Title
ES2784777T3 (en) Lithium-air battery
CN103579719A (en) Electrolyte for lithium air battery and lithium air battery composed thereof
US8981723B2 (en) Air battery system
JP5553072B2 (en) Liquid hydrophobic phase change material and battery using the same
US20070259234A1 (en) Metal-air semi-fuel cell with an aqueous acid based cathode
CN103069626B (en) Liquid air electrode for metal-air battery and metal-air battery provided with same
US20110229757A1 (en) Power storage device
WO2020259480A1 (en) Lithium primary battery
CN105322250A (en) Lithium-air battery with sodium salt as mediator
JP2006147392A (en) Battery
US9917339B2 (en) Non-aqueous lithium-air battery
US9653729B2 (en) Lithium carbon monofluoride-oxygen battery and method of using the same
EP2852993A1 (en) Process for producing a carbon-supported manganese oxide catalyst and its use in rechargeable lithium-air batteries
US20150318590A1 (en) Non-aqueous electrolyte solutions and lithium/oxygen batteries using the same
CN102956912A (en) Novel large-volume primary lithium liquid flow storage battery
KR20150026969A (en) Electrolyte solution for zinc air battery and zinc air battery comprising the same
US9318783B2 (en) Positive electrode for lithium air battery, method of preparing same, and lithium air battery including same
CN103579715A (en) Button lithium air battery capable of working in air
KR20140088902A (en) Rechargeable electrochemical cells
US20140147755A1 (en) Metal air battery
CN102280649A (en) Lithium primary cell
CN107910568A (en) A kind of lithium primary cell
CN108054376A (en) Seleno composite material is used as application of the positive electrode active materials in barium ions battery, barium ions battery and preparation method thereof
CN105355844B (en) Water-injection power generation environment-friendly battery and positive electrode and battery pack thereof
KR20150030997A (en) Electrolyte for aluminium air battery and aluminium air battery comprising the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140212

WD01 Invention patent application deemed withdrawn after publication