CN101107733B - Electrolyte compositions for batteries using sulphur or sulphur compounds - Google Patents

Electrolyte compositions for batteries using sulphur or sulphur compounds Download PDF

Info

Publication number
CN101107733B
CN101107733B CN200680002591XA CN200680002591A CN101107733B CN 101107733 B CN101107733 B CN 101107733B CN 200680002591X A CN200680002591X A CN 200680002591XA CN 200680002591 A CN200680002591 A CN 200680002591A CN 101107733 B CN101107733 B CN 101107733B
Authority
CN
China
Prior art keywords
lithium
sulphur
alkali metal
solvent
active material
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.)
Active
Application number
CN200680002591XA
Other languages
Chinese (zh)
Other versions
CN101107733A (en
Inventor
弗拉迪米尔·克洛什尼特斯
叶莲娜·卡拉塞娃
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.)
Johnson Matthey PLC
Original Assignee
Oxis Energy Ltd
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 Oxis Energy Ltd filed Critical Oxis Energy Ltd
Priority claimed from PCT/GB2006/000103 external-priority patent/WO2006077380A2/en
Publication of CN101107733A publication Critical patent/CN101107733A/en
Application granted granted Critical
Publication of CN101107733B publication Critical patent/CN101107733B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

There are disclosed electrolytes comprising solutions of lithium salts with large anions in polar aprotic solvents with a particular concentration of background salts. The concentration of the background salts is selected to be equal or close to the concentration of a saturated solution of these salts in the aprotic solvents used. The electrolytes disclosed can be used in chemical sources of electric energy such as secondary (rechargeable) cells and batteries comprising sulphur-based positive active materials. The use of such electrolytes increases cycling efficiency and cycle life of the cells and batteries.

Description

Improvement about the electrolyte composition of the battery that uses sulphur or sulphur compound
Technical field
The present invention relates to comprise the electrolyte composition that is used for chemical power source of positive pole (negative electrode) and negative pole (anode).Especially, embodiment of the present invention relate to rechargeable (secondary) battery, it comprises the negative pole (being made by lithium, sodium or another active material or composition) (anode) that ion is provided, contain the intermediate isolating element of liquid or gel electrolyte solution and contain sulphur as electrode depolarization material (active material of cathode), based on the positive pole (negative electrode) of the organic or inorganic compound of sulphur, the ion in charge or discharge cycle period of battery from the source electrode material moves between battery electrode by described intermediate isolating element.Embodiment of the present invention also relate to and contain described electrolytical chemical power source.Other embodiment of the present invention relates to the composition of electrolyte system, and it contains nonaqueous aprotic solvent, lithium salts and property-modifying additive and is designed to lithium-sulfur cell.
Background of invention
In this application, quote by identification and relate to various patents and disclosed patent application.The disclosure that content disclosed by the invention is introduced the patent that relates in this application and disclosed patent application as a reference, to describe prior art involved in the present invention more fully.
Make the electroactive material that is used for battery structure and be known as electrode.Be known as in this article in the battery of chemical power source and use in the pair of electrodes, be called as positive pole at electrode with higher one side, or negative electrode, and be called as negative pole at electrode with low electrochemical potential one side, or anode.
The electrochemical active material that is used for negative electrode or positive pole is called as active material of cathode hereinafter.The electrochemical active material that is used for anode or negative pole is called as active material of positive electrode hereinafter.Have electro-chemical activity and comprise electrochemical active material and optional electronic conductive additive and the multi-component combination of adhesive and other optional additive are called as electrod composition hereinafter.Comprising the chemical power source that has the negative electrode that is in the oxidation state active material of cathode and be in the anode of going back the ortho states active material of positive electrode or battery is called as and is in charged state.Correspondingly, comprise and have the chemical power source that is in the negative electrode of going back the ortho states active material of cathode and is in the anode of oxidation state active material of positive electrode and be called as and be in discharge condition.
Being dissolved in solvent or the solvent mixture mixture with lithium, sodium or other alkali metal salt or these salt of keeping solution conductivity is called as and supports salt (supporting salt).
The multiple electroactive material that has the cathode active layers that can be used for chemical power source.For example, in No. the 5th, 919,587, people's such as Mukherjee the United States Patent (USP) multiple above-mentioned electroactive material has been described.Proportion (the g/cm of these electroactive materials 3) and specific capacity (mAh/g) alter a great deal, so in these cathode active layers with mg/cm 3The intended volume density of the electroactive material of expression correspondingly in very large range changes.High expectations lithium and sulphur content is as the anode of chemical power source and the electrochemical active material of negative electrode, because based on the weight and volume of any known combination of active material, they provide almost is the highest possible energy density.In order to obtain high energy density, lithium can simple metal, alloy or embedding form exist, and sulphur can elementary sulfur or with high sulfur content, the form that preferred sulfur content is higher than the organic or inorganic material component of 75% weight ratio exists.For example, with the lithium anode combination, elementary sulfur has the specific capacity of 1680mAh/g.This height ratio capacity is special expectation for the application such as portable electron device and motor vehicle, and wherein the low weight of battery is very important.
Solution with the independent proton-inert polar solvent of macroanion lithium salts or solvent mixture is widely used as the electrolyte in lithium and the lithium ion chargeable battery.These electrolytical major requirements are:
High conductivity;
In big temperature range, be in the ability of liquid state or gel (gel electrolyte) attitude;
High stability to electrode active material;
Chemistry and electrochemical stability (wide electrochemical stability zone);
Fire prevention and explosive risk;
Nontoxic.
In above-mentioned requirement, the high conductivity in wide temperature range is main.Electrolytical conductivity is to be determined by the physics of solvent and salt and chemical characteristic.In order to obtain high conductivity, the preferred use has high power supply sub-feature, high-k and low viscous solvent, thereby provides the high dielectric degree of dissociation for lithium salts.The preferred use has the macroanion lithium salts, because it has high dissociating power.
The conductivity of salting liquid is by its concentration decision.Along with the rising of salinity, conductivity at first raises, and arrives maximum and final the reduction then.The concentration of salt is chosen as the gained electrolyte usually maximum conductivity [lithium battery: Science and Technology (science and technology), Gholam-Abbas Nazri and Gianfranco Pistoia (Eds.) Kluwer AcademicPublished2004.pp.509-573.] is provided.
The solution that one or more lithium salts form in independent solvent or solvent mixture also is used as electrolyte [United States Patent (USP) the 6th, 030, No. 720, Chu et al.] in lithium-sulfur cell.When designing electrolyte for lithium-sulfur cell, choice of Solvent is a subject matter, because the character of solvent (physics and chemical property) has material impact to the characteristic of battery.
The electrolytic salt that uses in main lithium of the prior art and the lithium ion battery can be used as the support salt in the lithium-sulfur cell.Usually, the patent disclosure of the prior art known to the applicant is not offered suggestions to specific preferred salinity, but possible concentration is provided a very wide scope.
Think at present and described immediate prior art in people's such as Hwang No. the 6th, 613,480, the United States Patent (USP) with the present invention.The information of this patent disclosure is that the electrolytic salt that is used for lithium-sulfur cell can be selected from down and compiles a name list: lithium hexafluoro phosphate (LiPF 6), hexafluoroarsenate lithium (LiAsF 6), lithium perchlorate (LiClO 4), two (trifyl) imines lithium (LiN (CF 3SO 2) 2)) and three fluosulfonic acid lithium (CF 3SO 3Li).The concentration of electrolyte salt should be 0.5M to 2.0M.
High conductivity in big temperature range (also having electrochemical stability) is the major requirement to the electrolyte composition that uses in lithium with traditional hard active material of cathode and the lithium ion battery.The selection difficulty more that is used for the electrolyte composition of lithium-sulfur cell because sulphur may be dissolved in the electrolyte solvent and with its component reaction, this can have material impact to characteristic of battery.
Although existing multiple electrolyte solvent and electrolytic salt are proposed to be used in rechargeable battery, still need improved non-aqueous electrolyte combination badly, it provides beneficial effect in useful life based on the chemical power source of the positive electrode active materials of sulphur for containing.
Therefore embodiment of the present invention seek to provide the improved non-aqueous electrolyte combination that is applicable to that rechargeable battery uses, and it contains based on the positive electrode active materials of sulphur and higher temperature stability is arranged and conductivity and higher battery cycle efficieny and long battery cycle life is provided.
Summary of the invention
Embodiment of the present invention relate to the electrolyte that is used for lithium-sulfur cell, for example contain the macroanion lithium salts forms solution in aprotic solvent electrolyte, and it has predetermined support salinity.Especially, embodiment of the present invention mixture that lithium salts or lithium salts be provided is equaling substantially or forming application in the electrolyte of concentration of saturated solution at least near lithium salts (or multiple lithium salts) in solvent (or solvent mixture).The use of this electrolyte in lithium-sulfur cell provides improved efficient and circulation timei.
According to a first aspect of the invention, it is provided for the electrolyte composition based on the chemical power source of sulphur, this electrolyte composition comprises at least a nonaqueous aprotic solvent and at least a alkali metal salt, wherein select described electrolyte composition, make the concentration of described at least a salt equal substantially or the approaching saturated concentration of described at least a alkali metal salt in described at least a solvent.
Preferably, the concentration of described at least a salt is at least 90% of described saturated concentration, preferably at least 95%, and even more preferably at least 99%.
Described at least a salt can be the independent salt or the mixture of alkali metal salt.Preferred especially lithium salts, but also can use sodium salt and other alkali metal salt or its mixture.
The example of lithium salts comprises lithium hexafluoro phosphate (LiPF 6), hexafluoroarsenate lithium (LiAsF 6), lithium perchlorate (LiClO 4), two (trifyl) imines lithium (LiN (CF 3SO 2) 2)) and three fluosulfonic acid lithium (LiCF 3SO 3).
Described at least a aprotic solvent can be independent following solvent or its mixture of being selected from: oxolane, 2-methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, methyl-propyl propionic ester, ethyl propyl propionic ester, methyl acetate, ethyl acetate, propyl acetate, dimethoxy-ethane, 1,3-dioxolanes, diethylene glycol dimethyl ether (2-methyl ethyl ether), tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, gamma-butyrolacton, sulfolane and at least a sulfone.
According to a second aspect of the invention, it provides a kind of chemical power source, it comprises negative pole (anode), anodal (negative electrode) and intermediate isolating element, described negative pole comprises the active material of positive electrode that is used to provide ion, described positive pole comprises and contains sulphur, active material of cathode based on the organic or inorganic compound of sulphur, described intermediate isolating element contains liquid or gel electrolyte solution, move to positive pole from the ion of negative pole by described intermediate isolating element in charge or discharge cycle period of chemical power source, wherein said electrolyte solution solution contains the described electrolyte composition of first aspect present invention.
Chemical power source can be battery or battery pack.
Active material of positive electrode can comprise the alkali metal such as lithium or sodium, or another active material or composition.
Particularly preferred active material of positive electrode comprises lithium metal, lithium alloy, sodium metal, sodium alloy, alkali metal or its alloy, metal dust, alkali metal-carbon and alkali metal-graphite insert, can be reversibly by the compound of alkali metal ion oxidation and reduction or their mixture.
The sulphur active material of cathode that contains can be selected from: elementary sulfur, many lithium sulfide (Li 2S nN 〉=1), based on non-organic or organic (comprising oligomer and the polymer) compound and their mixture of sulphur.
Active material of cathode can also comprise adhesive and electric conducting material.
Detailed description of the invention
When the design lithium-sulfur cell, capacity attenuation and relatively low cycle efficieny are the subject matter of running into rapidly.The irreversible migration that sulphur is surperficial from anodal (negative electrode) to negative pole (anode) and be one of the main reasons with the accumulation of lithium sulfide or curing lithium form there at lithium-sulfur cell cycle period capacity attenuation.The low cycle efficieny of lithium-sulfur cell is to be caused by sulphur irreversible migration of sulphur in charging and discharge process.This migration causes known sulfide circulation, and promptly the energy in the battery shifts (within it in the portion loop).
The end product (lithium sulfide or curing lithium) of known elements sulphur and sulphur reduction is insoluble in most of organic solvents.On the contrary, many lithium sulfides (at reduction elements sulphur or the intermediate product that produces in oxidation of sulfureted lithium or curing lithium process) are soluble in multiple organic solvent.
At the positive pole of lithium-sulfur cell and the sulphur migration rate between negative pole is to be determined by the form that is present in the sulphur in the electrolyte solution.The form that is present in sulphur in the electrolyte of lithium-sulfur cell and lithium-sulphur compound depends on that electrolyte system forms and characteristic.Especially, it depends on the concentration of employed polarity of solvent and power supply sub-feature and support salt.
Many lithium sulfides can following three kinds of forms be present in the electrolyte system: molecule, single anion and dianion.Therefore the sulphur in the electrolyte can be with molecule (neutrality) or the migration of ion (anion) form.The diffusion that is dissolved in many lithium sulfides of elementary sulfur in the electrolyte and non-disassociation helps the molecular migration of sulphur.The list of polysulfide and dianion, and the diffusion of sulphur anion base and electromigration help the sulphur migration of ionic species.The existence of these two kinds of mechanism has improved whole sulphur migration.Compare in pure diffusion mechanism, the sulphur migration in diffusion-transition process is higher.Therefore, the capacity attenuation speed of lithium-sulfur cell and cycle efficieny depend on that the form and the sulphur that are present in the sulphur in the electrolyte solution moves to inter-electrode space and the form from this to negative terminal surface from positive pole.If sulphur exists with neutral particle (molecular forms) rather than with the form of charged particle (ionic species), the capacity attenuation speed of lithium-sulfur cell can reduce and its cycle efficieny can improve greatly greatly so.
The degree of ionization of every kind of salt in electrolyte solution determined by concentration separately that has two or more different salt (for example being many lithium sulfides and support salt at this) in electrolyte composition and electrolysis constant.Based on relevant anionic character, the applicant believes that the dissociation constant of many lithium sulfides is more much lower than the dissociation constant that can be used as most of lithium salts of supporting salt.In this case, along with the rising of the concentration of supporting salt, the balance in the dissociation reaction of many lithium sulfides can move to the direction that has polymolecular form more rather than ionic species.
Therefore, the degree of dissociation of many lithium sulfides reduces along with the rising of the concentration of supporting salt.Therefore, can find that the sulphur migration rate between the electrode will reduce, and correspondingly, the capacity attenuation speed of lithium-sulfur cell also will reduce cycle period in its.In addition, as the result that the sulfide cycle rate reduces, cycle efficieny should improve.This has in the following example clearly and shows.
When forming the electrolyte composition of embodiment of the present invention, should consider following factors:
1) electrolyte composition should comprise nonaqueous aprotic solvent, lithium or another alkali metal salt and optional property-modifying additive.
2) described salt can be independent salt or multiple different salt.
3) described salt or multiple salt are dissolved in the independent proton-inert polar solvent or solvent mixture.
4) should select described electrolyte composition, make the concentration of mixture of lithium salts or salt equal the concentration of the saturated solution of one or more salt used in (or approaching) solvent or the solvent mixture.
In order to understand the present invention better and to show how it implements, exemplarily with reference to the accompanying drawings, wherein:
Fig. 1 is the figure of charging and the discharge capacity decay of display standard lithium-sulfur cell cycle period;
Fig. 2 is the figure of the lithium-sulfur cell of display standard in cycle efficieny and capacity attenuation rate variation;
Fig. 3 shows that the cycle period with electrolytical second lithium-sulfur cell of higher concentration charges and the figure of discharge capacity decay;
Fig. 4 is the figure that shows the second lithium-sulfur cell cycle efficieny and capacity attenuation rate variation;
Fig. 5 is the figure of demonstration according to charging and the discharge capacity decay of the cycle period of the 3rd lithium-sulfur cell with saturated electrolytic solution of embodiment of the present invention;
Fig. 6 is the figure that shows the 3rd lithium-sulfur cell cycle efficieny and capacity attenuation rate variation;
Fig. 7 shows to have the figure that cycle period charges and discharge capacity decays different, electrolytical the 4th lithium-sulfur cell of unsaturation;
Fig. 8 is the figure that shows the 4th lithium-sulfur cell cycle efficieny and capacity attenuation rate variation;
Fig. 9 is the figure that cycle period charges and discharge capacity decays that shows according to the 5th lithium-sulfur cell with saturated electrolytic solution of embodiment of the present invention; And
Figure 10 is the figure that shows the 5th lithium-sulfur cell cycle efficieny and capacity attenuation rate variation.
Embodiment 1
By assembling the anode made from metallic lithium foil; Porous barrier Celgard
Figure S06802591X20070720D000071
2500 (registered trade mark of Celgard Inc. can be buied from the Celgard K.K. of Tokyo, can also buy from the Celgard Inc. of North Carolina South Lakes); The sulphur negative electrode that contains elementary sulfur (70% weight ratio) as depolarizing agent, carbonaceous conductive additive (10% weight ratio) Ketjenblack
Figure S06802591X20070720D000072
EC-600JD (can buy) from the Akzo Nobel Polymer ChemicalsBV of Holland, and adhesive (molecular weight is 4000000 polyethylene glycol oxide, 20% weight ratio) obtains lithium-sulfur cell.By automatic film applicator Elcometer
Figure S06802591X20070720D000073
SPRL as the aluminium foil of the coating 18 micron thickness conductive carbon of current-collector and substrate (from the InteliCoat of Massachusetts South Hadley
Figure S06802591X20070720D000074
Buy) a side on deposition sulphur negative electrode.The specific surface capacity of negative electrode is 1mAh/cm 2Use contains 0.1M LiClO 4The electrolyte of sulfolane solution fill the battery of assembling.Battery assembling and each stage of filling carry out in " Jacomex BS531 type " glove box.Charging and discharge rate and cycle battery under 25 ℃ temperature with 0.25C.Cycle period battery charging and the variation of discharge capacity as shown in Figure 1.
Cycle period cycle efficieny and the capacity attenuation rate variations as shown in Figure 2.With the discharge capacity represented with percentage and the efficient of computation cycles recently of charging capacity.Capacity volume variance with two adjacent circulations is come the calculated capacity rate of decay divided by the average size in these circulations, represents with percentage.As can be seen from Figure 2, the beginning after circulation beginning of cycle efficieny and capacity attenuation speed changes, but stable after a while.Average cycle efficieny between the 10th and the 20th circulation is 68%, and capacity attenuation speed is 4.5%.
Embodiment 2
As production lithium-sulfur cell as described in the embodiment 1, contain 1M LiClO but at this moment use 4The electrolyte of sulfolane solution fill the battery of assembling.Charging and discharge rate and cycle battery under 25 ℃ temperature with 0.25C.Cycle period, the charging and the discharge capacity of battery changed as shown in Figure 3.
Cycle period cycle efficieny and the capacity attenuation rate variations as shown in Figure 4.As can be seen from Figure 4, the beginning after circulation beginning of cycle efficieny and capacity attenuation speed changes, but stable after a while.Average cycle efficieny between the 10th and the 20th circulation is 90%, and capacity attenuation speed is 2.25%.This is significant an improvement for the battery of relative embodiment 1.
Embodiment 3
As production lithium-sulfur cell as described in the embodiment 1, contain 2M LiClO but at this moment use according to embodiment of the present invention 4The electrolyte of saturated sulfolane solution fill the battery of assembling.Charging and discharge rate and cycle battery under 25 ℃ temperature at 0.25C.Cycle period, the charging and the discharge capacity of battery changed as shown in Figure 5.
Cycle period cycle efficieny and the capacity attenuation rate variations as shown in Figure 6.As can be seen from Figure 6, the beginning after circulation beginning of cycle efficieny and capacity attenuation speed changes, but stable after a while.Average cycle efficieny between the 10th and the 20th circulation is 96%, and capacity attenuation speed is 1.75%.Relatively embodiment 1 and 2 battery this be significant an improvement.
Embodiment 4
As production lithium-sulfur cell as described in the embodiment 1, contain 0.1M LiClO but at this moment use 4The electrolyte of methyl propyl sulfone solution fill the battery of assembling.Charging and discharge rate and cycle battery under 25 ℃ temperature with 0.25C.Cycle period, the charging and the discharge capacity of battery changed as shown in Figure 7.
Cycle period cycle efficieny and the capacity attenuation rate variations as shown in Figure 8.As can be seen from Figure 8, the beginning after circulation beginning of cycle efficieny and capacity attenuation speed changes, but stable after a while.Average cycle efficieny between the 10th and the 20th circulation is 55%, and capacity attenuation speed is 3.1%.
Embodiment 5
As production lithium-sulfur cell as described in the embodiment 1, but at this moment use the LiClO that contains 1.7M 4The electrolyte of methyl propyl sulfone solution (concentration is near saturated solution) fill the battery of assembling.Charging and discharge rate and battery under 25 ℃ temperature cycles with 0.25C.Cycle period battery charging and the variation of discharge capacity as shown in Figure 9.
Cycle period cycle efficieny and the capacity attenuation rate variations as shown in Figure 8.As can be seen from Figure 8, the beginning after circulation beginning of cycle efficieny and capacity attenuation speed changes, but stable after a while.Average cycle efficieny between the 10th and the 20th circulation is 90%, and capacity attenuation speed is 1.15%, and the battery of embodiment 4 is significant an improvement relatively.
Embodiment 4 and 5 shows that the improvement of cycle efficieny and capacity attenuation speed does not rely on the chemical characteristic of solvent, but depends on electrolytical concentration.
Though illustrated and described certain embodiments of the present invention, should be understood that to the invention is not restricted to these specific embodiments.Under the situation that does not depart from the scope of the invention, the person of ordinary skill in the field can carry out multiple improvement, variation, change, substitutes and be equal to replacement to it.
Preferable feature of the present invention is suitable for all aspects of the present invention, and can be used among any possible combination.
In the description and claim of this specification, word " comprises (comprise) " and " containing (contain) " and variation thereof, for example " comprise (comprising) " and " comprising (comprises) " meaning is " including but not limited to ", and do not plan (and not) get rid of other composition, integer, partly, additive or step.

Claims (10)

1. be used for electrolyte composition based on the chemical power source of sulphur, described electrolyte composition comprises at least a nonaqueous aprotic solvent and at least a alkali metal salt, wherein select described electrolyte composition, make the concentration of described at least a alkali metal salt in described at least a solvent be at least 90% of its saturated concentration, prerequisite is that described at least a alkali metal salt is unsaturated in described at least a solvent.
2. electrolyte composition as claimed in claim 1, wherein said at least a solvent is selected from: oxolane, 2-methyltetrahydrofuran, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, methyl-propyl propionic ester, ethyl propyl propionic ester, methyl acetate, ethyl acetate, propyl acetate, dimethoxy-ethane, 1,3-dioxolanes, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, gamma-butyrolacton and at least a sulfone.
3. electrolyte composition as claimed in claim 1 or 2, wherein said at least a alkali metal salt is selected from: lithium hexafluoro phosphate (LiPF 6), hexafluoroarsenate lithium (LiAsF 6), lithium perchlorate (LiClO 4), two (trifyl) imines lithium (LiN (CF 3SO 2) 2), three fluosulfonic acid lithium (LiCF 3SO 3) or their mixture.
4. electrolyte composition as claimed in claim 1, the concentration of wherein said at least a alkali metal salt in described at least a solvent is at least 95% of its saturated concentration.
5. electrolyte composition as claimed in claim 1, the concentration of wherein said at least a alkali metal salt in described at least a solvent is at least 99% of its saturated concentration.
6. chemical power source, it comprises negative pole (anode), anodal (negative electrode) and intermediate isolating element, described negative pole comprises the active material of positive electrode that is used to provide ion, described positive pole comprises and contains sulphur or contain active material of cathode based on the organic or inorganic compound of sulphur, described intermediate isolating element contains liquid or gel electrolyte solution, move to positive pole from the ion of negative pole by described intermediate isolating element in charge or discharge cycle period of chemical power source, wherein said electrolyte solution comprises the described electrolyte composition of arbitrary claim in the claim 1 to 5.
7. chemical power source as claimed in claim 6, the active material of cathode of wherein said sulfur-bearing is selected from: elementary sulfur, based on the inorganic compound of sulphur, based on the organic compound of sulphur and their mixture, wherein said inorganic compound based on sulphur is lithium sulfide or general formula Li 2S nMany lithium sulfides, n 〉=2 wherein.
8. as claim 6 or 7 described chemical power sources, wherein also in the active material of cathode of described sulfur-bearing, add adhesive and electric conducting material.
9. as claim 6 or 7 described chemical power sources, wherein said active material of positive electrode is selected from: alkali metal or its alloy, metal dust, alkali metal-carbon insert, can be reversibly by the compound of alkali metal ion oxidation and reduction and their mixture.
10. chemical power source as claimed in claim 8, wherein said active material of positive electrode is selected from: alkali metal or its alloy, metal dust, alkali metal-carbon insert, can be reversibly by the compound of alkali metal ion oxidation and reduction and their mixture.
CN200680002591XA 2005-01-18 2006-01-11 Electrolyte compositions for batteries using sulphur or sulphur compounds Active CN101107733B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB0501001.2 2005-01-18
GB0501001A GB2422244B (en) 2005-01-18 2005-01-18 Improvements relating to electrolyte compositions for batteries using sulphur or sulphur compounds
US65276905P 2005-02-15 2005-02-15
US60/652,769 2005-02-15
PCT/GB2006/000103 WO2006077380A2 (en) 2005-01-18 2006-01-11 Improvements relating to electrolyte compositions for batteries using sulphur or sulphur compounds

Publications (2)

Publication Number Publication Date
CN101107733A CN101107733A (en) 2008-01-16
CN101107733B true CN101107733B (en) 2010-07-21

Family

ID=34224777

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200680002591XA Active CN101107733B (en) 2005-01-18 2006-01-11 Electrolyte compositions for batteries using sulphur or sulphur compounds

Country Status (3)

Country Link
CN (1) CN101107733B (en)
ES (1) ES2677021T3 (en)
GB (1) GB2422244B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2438890B (en) * 2006-06-05 2011-01-12 Oxis Energy Ltd Lithium secondary battery for operation over a wide range of temperatures
US9525196B2 (en) * 2012-04-02 2016-12-20 Sumitomo Seika Chemicals Co., Ltd. Electrolyte solution for lithium air batteries, and lithium air battery
EP2784850A1 (en) * 2013-03-25 2014-10-01 Oxis Energy Limited A method of cycling a lithium-sulphur cell
KR20190125740A (en) * 2018-04-30 2019-11-07 주식회사 엘지화학 Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1178555A2 (en) * 2000-08-02 2002-02-06 Samsung SDI Co., Ltd. Lithium-sulfur batteries

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100322449B1 (en) * 1999-06-07 2002-02-07 김순택 Electrolyte for lithium secondary battery and lithium secondary battery using the same
KR100467456B1 (en) * 2002-09-10 2005-01-24 삼성에스디아이 주식회사 Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same
KR100472513B1 (en) * 2002-11-16 2005-03-11 삼성에스디아이 주식회사 Organic electrolytic solution for Lithium sulfur battery and Lithium sulfur battery appling the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1178555A2 (en) * 2000-08-02 2002-02-06 Samsung SDI Co., Ltd. Lithium-sulfur batteries

Also Published As

Publication number Publication date
GB2422244B (en) 2007-01-10
GB0501001D0 (en) 2005-02-23
CN101107733A (en) 2008-01-16
GB2422244A (en) 2006-07-19
ES2677021T3 (en) 2018-07-27

Similar Documents

Publication Publication Date Title
JP5651284B2 (en) Lithium-sulfur battery
TWI393284B (en) Substituted phenothiazine redox shuttles for rechargeable lithium-ion cell, rechargeable lithium-ion cell, and method for manufacturing rechargeable lithium-ion sealed cell
JP5466364B2 (en) Lithium / sulfur battery electrolyte and lithium / sulfur battery using the same
CN1288789C (en) Electrolyte for lithium secondary battery and lithium secondary battery containing the same
US20210005937A1 (en) ELECTROLYTES FOR RECHARGEABLE Zn-METAL BATTERY
CN101997145B (en) Lithium sulfur battery
KR101108945B1 (en) Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same
US9023518B2 (en) Lithium—sulfur battery with performance enhanced additives
CN103151554B (en) Lithium-sulfur cell
JP2008522376A5 (en)
CN104835982B (en) Electrolyte composition for lithium-sulfur cell
CN105830258A (en) A lithium-sulphur cell
CN100474682C (en) Organic electrolytic solution and lithium-sulfur battery comprising the same
CN101084595B (en) Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same
CN101107733B (en) Electrolyte compositions for batteries using sulphur or sulphur compounds
KR100736909B1 (en) Nonaqueous electrolyte for lithium battery and lithium secondary battery comprising the electrolyte
CN201536138U (en) Lithium-sulfur battery
JP4076748B2 (en) Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery
JP4076726B2 (en) Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery
JP2600175B2 (en) Rechargeable battery
CN116315113A (en) High-voltage quick-charging electrolyte and double-ion battery
JP4076735B2 (en) Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery
Tsunashima et al. An Organic Electrolyte Mixed with a Quaternary Phosphonium Salt for Lithium Secondary Batteries
Rajagopalan et al. Zinc-Ion Batteries: A Promising Solution for Future Energy Demands
Eisenhart Innovation in Lithium-Ion Battery Technology

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20220608

Address after: London

Patentee after: JOHNSON MATTHEY PLC

Address before: oxford

Patentee before: OXIS ENERGY Ltd.

TR01 Transfer of patent right