CN1023364C - Cell for making secondary batteries - Google Patents

Cell for making secondary batteries Download PDF

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CN1023364C
CN1023364C CN90109212A CN90109212A CN1023364C CN 1023364 C CN1023364 C CN 1023364C CN 90109212 A CN90109212 A CN 90109212A CN 90109212 A CN90109212 A CN 90109212A CN 1023364 C CN1023364 C CN 1023364C
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battery
sulphur
negative electrode
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anode
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CN1053324A (en
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斯蒂芬·J·维斯科
刘美玲
卢特加德·C·德容格
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University of California
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    • H—ELECTRICITY
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    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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    • 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
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    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145 DEG C (limited by melting points or electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode (12), a polymeric electrolyte (15) such as polyethylene oxide doped with lithium triflate (PEO8LiCF3SO3), and a solid-state composite positive electrodes (14) containing a polymeric organosulfur electrode, (SRS)n, and carbon black, dispersed in a polymeric electrolyte.

Description

Cell for making secondary batteries
Invention described herein is to produce in the process of USDOE and the signing DE-AC03-76SF00098 of Gary Fu Niya university contract and under the regulation at this contract, so U.S. government enjoys rights to this invention.
The metal sulphur type battery that the present invention relates to make secondary battery is its whole compositions battery of all carrying out work under solid state particularly.
Modern society is extensive use of secondary battery, need not under the situation of a large amount of energy to use outstanding wide.But need to use battery pack still very desirable aspect the higher power applications at some.Carry out extensive work development and be applicable to the battery pack that high power such as motor vehicle need.Certainly these battery pack also are applicable to low-power purposes such as camera, portable type sound pick-up outfit etc.
Present prevailing secondary battery may be the lead-acid battery that is used for automobile.The advantage of this kind battery does not have big loss for carrying out repeatedly charging cycle on performance.This kind energy content of battery is very low to the ratio of weight, in order to promote energy to weight ratio, lithium battery has been carried out comprehensive investigation, and some systems in this type systematic get a good chance of on some purposes.Owing to done to apply after improvement can be thought biglyyer.
Lithium polyethylene oxide battery is developed and drawn a typical performance index (FOM), and this calculates by following process: multiply by average circulation volume with cycle-index, divided by set excessive lithium capacity, this performance index is about 50 again.Can see such battery in No. 4,589,197, the United States Patent (USP) of narration lithium/polyethylene battery system, electroactive material is one and embeds compound (intercalation compound) in this system.Such battery shows that also the size that can scale up does not have any significant performance loss.
United States Patent (USP) 4,833 is mentioned another kind of lithium type battery No. 048, and this battery uses an organic sulfur positive electrode, and the sulphur-sulfide linkage in its charged state is broken up into organic metal salt in discharge condition.This patent disclosure a kind of battery with good energy to weight ratio, but the disclosed electrode of this kind uses in liquid state, needs solvent just can provide required electric current to carry.The present invention improves these systems that obtain patent, the invention provides a kind of performance index grade specifically and be 120 battery, can use under the situation of room temperature or ambient temperature.
Therefore, main purpose of the present invention is to provide a kind of metal sulphur type battery with high-performance index, can use at ambient temperature.
A purpose of the present invention is solid-state for providing a kind of its all parts all to belong to, and can be assembled into the battery with regenerability unit reliably by them.
A further object of the present invention is much higher than the demand that load level and/or motor vehicle use for its energy to weight ratio of a kind of battery is provided.
These purposes and other purposes will be shown fully aware ofly in the following description.
The battery system that a kind of synthetic positive electrode can be provided according to the present invention and constitute with this synthetic positive electrode system.This positive electrode comprises one one dimension, two dimensions or the electroactive composition of three-dimensional polymerization under complete charge condition.In a dimension linear form, this composition can constitute (SRS) n, wherein R is an organic moiety, will be illustrated below, n is greater than 2, under charge condition to be advisable greater than 20: half-cell reaction can be described below:
（SRS） n+2ne＝n-SRS-
Full cell reaction can be described below:
（SRS） n+2nLi＝nLi 2SRS
Say on the just general meaning that the electroactive composition of solid-state organic sulfur electrode can (RSy) when charging nExpression, wherein Y is a numeral of 2 to 6; N is greater than 2, with more suitable greater than 20; R is one or more different aliphatic series or the aromatics part with 1 to 20 carbon atom, and when R comprised one or more aromatic rings, R may comprise one or more oxygen, phosphorus, silicon, sulphur or nitrogen heteroatom; When R comprised an aliphatic chain, R may comprise the chain association therewith of one or more oxygen, phosphorus, silicon, sulphur, nitrogen or fluorine atom, and aliphatic series may be straight chain or branch key, saturated shape or unsaturation shape in this chain.Aliphatic chain or aromatic ring can have substituting group separately.In addition, the characteristics of above-mentioned organic sulfur positive electrode have a large amount of sulphur-sulfide linkages during for charged state, and when battery discharge status, these keys just break and form the organic metal salt that has metal ion in battery.
The charge/discharge process of this positive electrode can be considered a kind of reversible redox polymerization (or under the monomer RSSR compound situation, then being redox two polymerizations/split branch).The example of two dimensions (ladder polymer) electrode can be used polymine disulphide.
Be illustrated as follows:
Figure 901092126_IMG2
Though these polymerization electrode materials can transport alkaline metal ions, but must or preferably comprise a suitable polyeletrolyte as a rule, polyethylene oxide for example is so that transport ion rapidly, as the situation of the electrode that embeds type in electrode.In addition, because the organic sulfur electrode is non-conductive, be sought after in composite electrode dispenser a small amount of (be generally 7% weight) carbon ink or equal with it conductor particulate.Material in the polymerization positive electrode, with regard to weight, active organic sulfur is about 30% to 80%, and polyeletrolyte is about about 20% to 70%, and the conductor particulate is about about 1% to 20%.
Desirable mixture can be made with laxative remedy: (SRS) nPolymer, polyethylene oxide, hydrocarbon black powder dissolving or be sprinkling upon acetonitrile (CH 3CN) make the film (being about 10 to 200 microns) of solvent evaporation in subsequently to cause one deck solid composite electrode.Preferred situation is that positive electrode is one and comprises the organic sulfur redox polymers, the positive electrode of polyethylene oxide and carbon black.
Under the situation of charging fully, the organic sulfur positive electrode has general structural formula (SRS) n, its main feature is: constitute sulphur-sulfide linkage under alkalinous metal sulfo-salt oxidation situation.Preferred electrode is a kind of polymerization disulphide, but it is believed that at United States Patent (USP) 4,833, and the monomer disulphide of describing in No. 048 (RSSR) also can work in solid state battery.Under abundant discharge scenario, the organic sulfur electrode comprises many sulfo-s and/or two sulfo-anion, and (SRS-), they are scattered in the polyeletrolyte matrix.Certainly, last discharging product is decided by in the polymeric chain R types of radicals and the abundant dimension of the polymerization positive electrode of oxidation.
The performance that another advantage of the present invention is a solid state electrode is reversible to various metals.The advantage of lithium is that equivalent weight and relative weight are minimum, but price is more expensive than sodium.In addition, desirable polyether electrolyte such as polyethylene oxide are carried sodium than carrying lithium conductivity height.Therefore the embedded type battery needs lithium as viable material, and the available multiple metal of the negative electrode of electrode of the present invention constitutes.Therefore, (the polyether electrolyte has shown can transport bivalent cation such as Zn for alkalinous metal alkaline-earth metal or transition metal ++) any all genus within the scope of the invention, particularly comprise the mixture of lithium and/or sodium.
The electrolyte that uses in the battery of the present invention also transports media as metal ion as electrode separation agent usefulness.Therefore, as long as transporting metal ion, all can use any solid material.For example sodium just shows and can use.Yet, the solid electrolyte release agent is preferably used any suitable polyeletrolyte, for example polyether, poly-imines, many sulfo-s ether, polyphosphazene (polyphosphazenes), the material of polymeric blends and the like wherein adds suitable electrolyte salt.
Figure one is a battery critical piece profile constructed in accordance.
Figure two compares with the data of a diagrammatic representation device operational circumstances of the present invention and with the data of prior art same device.
The type of metal sulphur shown in the figure one battery comprises a current collector (11) near negative electrode (12), and the current collector (13) near positive electrode (14) is clipped in the electrolyte (15) between negative electrode (12) and the positive electrode (14).Typical battery situation is: all these parts all are closed within a suitable plastic (or similar material) the shell (not shown), have only current collector to stretch out outside the shell.Like this, just reactive metal in negative electrode such as sodium or lithium are protected, other parts of battery are protected too.
Technology according to needed battery of known assembling and battery component can be made suitable battery structure; And any known topography all can adopt the present invention to make, and mainly makes what purposes according to battery component and decides CONSTRUCTED SPECIFICATION.But should be familiar with each battery component and when ambient temperature is operated, all should be in real solid state.
With regard to figure one, current collector (11,13) is the conductive metal sheet of stainless steel and so on again, remains unchanged substantially under battery discharge and charge condition, and is the positive pole and the negative pole making current of battery.Negative electrode (12) is the alkalinous metal of lithium or sodium and so on preferably, and sodium is better than lithium.Organic sulfur negative electrode or positive electrode (14) set off as described above like that on current collector (13), and whole assembly abuts against together, and electrolyte is clipped between two electrodes as shown in the figure.
The thickness of each parts of battery has all strengthened so that diagram shows among the figure, and these component standards situations all are relatively thinner thin slices in fact.For example, the thickness of typical lithium or sodium solid anodes (12) is about the 10-50 micron, and the thickness of typical solid synthesized polymer negative electrode (14) is about the 50-100 micron, and the thickness of typical PEO electrolyte 15 is about the 10-100 micron.
Desirable electrolyte is a for example polyethylene oxide of polyalkylene oxides, wherein adds for example LiN(CF of plasticising electrolytic salt 3SO 2) 2The effectiveness of plasticising electrolytic salt is to keep polyether to be in amorphous (conduction) state when low temperature, thereby battery is worked at low temperatures.
According to the present invention, organosulfur compound constitutes the positive electrode of novelty of the present invention, be characterized in: the organic sulfur material has at least a sulphur atom and an organic moiety to form first key, and another sulphur atom also is combined into second key with an organic moiety when material is in charged state.When compound was in discharge condition, sulphur-sulfide linkage was broken, and metal ion is sodium for example, just and each organic anion that generates thus form salt.
Therefore positive electrode material comprises a kind of organic sulfur material with basic or backbone formula R-S-, under charge condition, sulphur atom (or a plurality of atom, describe in detail below) form one-S-S-key with the sulphur atom of another radicals R-S-, constitute R-S-S-R, during discharge, the S-S key breaks, and each R-S-base all constitutes salt (R-S-Na) with a metal (as sodium) ion.
The R base (later on again explain) of representing organic moiety not only as above say with the sulphur atom combination, also may be combined into R=S to sulphur atom in two key modes.The R base also may be an above sulphur atom with the combination of singly-bound mode, and this just might carry out polymerization, for example-and the situation of S-R-S-.When the R base have three or three above sulphur atoms with such singly-bound mode in conjunction with the time also branch's situation may appear.
Therefore, the general formula of organic sulfur material when charging with the new-type positive electrode of the present invention can be write as (R(S) Y) n, wherein Y is a number of 2 to 6, and n is greater than 20, and R is one or more identical or different aliphatic series or aromatics organic moiety, has the 1-20 carbon atom.When having one or more aromatic rings, R may comprise one or more oxygen, sulphur, phosphorus, silicon or nitrogen heteroatom; May comprise oxygen, phosphorus, silicon, sulphur, nitrogen or fluorine atom that one or more and this key associates when R has an aliphatic chain, wherein aliphatic series can be straight chain or branch chain, and saturated or unsaturation wherein has substituting group on aliphatic chain or the aromatic ring.
As general formula (R(S) y) nIn n greater than 2 o'clock, at least some organic sulfur positive electrode materials have the organic moiety that contains an above sulphur atom, are attached to the sulphur atom of same organic moiety and can form sulphur-sulfide linkage with the sulphur that is attached to another organic moiety.Like this under its charge condition, just a polymer-like material can form, the length of polymer depends on impurity or chain stopper such as monosulfide organic moiety (for example CH 3-CH 2-S-Na), they stop polymerization.Such polymer for example, may constitute the linear aliphatic chain that respectively there is such sulphur atom at two ends as-S-CH 2CH 2-S-is so that form dimer, oligomer like-S-CH 2-CH 2-S-S-CH 2-CH 2-S-S-CH 2-CH 2-S-meets general formula (R(S) 2) 3
Equally, organosulfur compound may have the branch chain polysulfide material that contains two above sulphur, can form sulphur-sulfide linkage with the sulphur atom on other organic sulfur materials that are close to.For example when each R base comprised three sulphur atoms that can constitute sulphur-sulfide linkage, general formula can be write as (R(S) 3) n
Therefore, it is 2 to 6 that the y in general formula decides its value, and this is to have recognized two kinds of possibilities, and one may be to have two key sulphur on the R base, and another kind may be that an above sulphur atom on it can be formed sulphur-sulfide linkage with the same sulphur atom on other molecules.N value in general formula is preferably greater than 20, but also decided one simultaneously and comprised 2 to 20 scope, this is to recognize that polymerization might be in the lower stage, for example forms ring, also is beneficial to because solid state battery has the organosulfur compound of not polymerization simultaneously.N value no maximum is because the character of employed organosulfur compound has limited the degree of polymerization under charge condition.
The redox chemistry process of organic sulfur electrode is at United States Patent (USP) 4,833, detailed explanation arranged in No. 048, and wherein relevant literal is in conjunction with being used as reference material.Although the organic sulfur electrode that the present invention uses is identical, the operation sequence when low temperature is solid-state is different with it.Therefore, the present invention preferably adopts the organic sulfur polymer of (better more than 50) monomeric unit more than 20.In addition, positive electrode of the present invention is different with the positive electrode in the above-cited patent, use be that special electric current transports additive.
The working temperature of solid state battery is between-40 to 145 ℃, and the upper limit is exceeded with one of two electrodes or electrolytical fusing point.Desirable temperature is between the ambient temperature to 100 ℃.The sodium negative electrode is limited to 98 ℃ of following temperature, but sodium alloy electrode such as Na 4Pb can substantially exceed 100 ℃ to be used in solid-state.
Employing solid polymer electrolyte and solid oxide reductive polymerization negative electrode just might be made all-solid-state battery, and do not produce and use difficulty solid-state firmly or that liquid electrolyte is relevant.The viscosity of solid-state polymerization electrolyte and solid oxide reductive polymerization negative electrode and elasticity have prevented the forfeiture that electrically contacts between battery cycle period solid electrolyte and electrode or have seriously weakened.In addition, the present invention improves prior art, promptly replaces some mordant liquid material with safe solid state component.This change is very easily made and is packed with regard to making battery available height automation process constructed in accordance, and battery does not have corrosiveness to container material yet.
Following laboratory tests illustration can further be illustrated the present invention.
The laboratory battery is with a sodium negative electrode, sodium beta-alumina electrolyte, and a usefulness (SRS) nThe positive electrode that polyethylene oxide and carbon particle are made.Employed (SRS) nPolymer is the polymer of one 2,5 dimercapto 1,3,4 thiadiazoles, below structure show three unit of this polymer:
Figure 901092126_IMG3
Synthetic positive electrode is cast about 100 micron thickness, and the surface is about 0.0115g/cm 2Electrode surface areas.100 microns polymer thin film active volumes are about 6.4 storehouses/cm 2Or 1.8mAh/cm 2The battery of assembling is recycled to 6 coulombs terminal point (being called 100% capacity).These batteries charge under the situation of all temps and current density and 80 circulations altogether of discharging, and definitely do not have the obvious sign of performance degradation.When 130 ℃ operating temperature, battery can be 4mA/cm in current density 2Shi Fangdian reaches 100% active volume, is 3mA/cm in current density 2In time, can be charged fully once more afterwards circulation do not produced bad influence.In addition, the discharge ratio of battery can be up to 10mA/cm 2Active volume than 50%, the charging ratio can be up to 6mA/cm concerning 65% active volume 2In addition, this extra high charge/discharge current density is not damaged the integrality of solid-state polymerization electrode.Even these achievements in research show solid oxide reductive polymerization electrode and also still have invertibity and reliability under abominable electrochemical conditions.
With lithium negative electrode, polyethylene oxide electrolyte, and with (SRS) nThe battery that the positive electrode of polymer, polyethylene oxide and carbon granules system constitutes is the actual performance that is used for testing hull cell constructed in accordance.The solid electrolyte that uses in these batteries is to coat lithium triflate(LiCF 3SO 3), lithium perchlorate (LiClO 4) or the polyethylene oxide of other suitable electrolytic salts.The concentration of electrolytic salt is divided alite 8PEO monomeric unit (CH for each 2CH 2O), be abbreviated as PEO herein 8LiX, wherein X is a salt anionic, just the same in employed organic sulfur polymer and the above-mentioned sode cell.
As mentioned above, synthetic positive electrode is made for the sodium base battery, and difference has been to cast the electrode of two kinds of thickness; High power capacity 6 storehouses/cm 2Film (100 microns) and low capacity 3 storehouses/cm 2Film (50 microns) is to adapt to the battery of high power density.This Li/PEO/[(SRS) n/ PEO/C] battery in theory energy density be 1000wh/kg, battery its actual energy density concerning the high power capacity film of assembling is 338wh/kg(zero power consumption) then 304wh/kg concerning the low capacity film, this is according to virtual electrode weight, the PEO film and 4: 1 excessive lithium (excess of actual battery lithium is bigger) obtain.These batteries are by two kinds of different degree of discharge chargings and discharge 350 circulations altogether.100 times circulation discharges reach the degree of depth of capacity 80%, and remaining 250 circulation discharges reach the degree of depth of capacity 50%.The power density and the energy density that show are high especially, surpass all known solid-state embedding compound base batteries, this point as can be seen from following form.This battery is better than the battery performance of working under the much higher situation of temperature, back one class battery such as Na/ βYang Hualv/S battery (350 ℃), Li/LiCl/KCl/FeS 2Battery (450 ℃) or the like.
The power power of the theoretic actual volume of battery title
Energy density energy density energy density density density
wh/kg wh/kg wh/l W/kg w/l
At 0 electric current 160 144
1000 o'clock is 300 280 350
Li/PEO/(SRS) 2(OCV=is in 0.5mA/ circulation 2200
3.0) cm 2350 follow 2,400 5 minutes
Be 1 to follow during ring
264 rings 100
The % profit
Use rate
Li/PEO/TiS 2480
（OCV＝ 120 150 100 1500
2.1) 5 seconds
Cd/NiOOH 245 35
Figure dual-purpose diagrammatic representation Li/PEO/X and Li/PEO/TiS 2Between correction data.Jc represents that the battery that charges, JD represent the battery that discharges among the figure.Test is to computerized control, and the peak load maximum is to print in of short duration dwell time, and therefore will get rid of these peak load maximums could obtain real data.Battery of the present invention as shown in the figure always can sustaining voltage at interdischarge interval, and battery has in contrast descended soon, battery of the present invention in addition since the negative electrode utilization rate can charge once more near 100%.
All higher from above-mentioned explanation battery provided by the present invention as can be seen than electric energy and specific power, surpass the battery of the high development system of known applications, high-energy and high power are applicable to room temperature or ambient temperature operation simultaneously.

Claims (20)

1, a kind of solid metallic sulphur battery, it comprises:
(a) solid metal anode;
(b) SOLID ORGANIC sulphur negative electrode, it comprises the polymer of (at Charging state) a kind of formula (R (S) y) n, Y=2-6 wherein, n is greater than 20, R is one or more identical or different aliphatic series with 1-20 carbon atom or aromatics part, when comprising one or more aromatic ring, R may contain one or more oxygen, sulphur or nitrogen heteroatom, when comprising aliphatic chain, R may contain one or more oxygen that associate with this chain, sulphur, nitrogen or fluorine atom, wherein aliphatic group can be a straight or branched, saturated or unsaturated, wherein may have substituting group on aliphatic chain or the aromatic ring, the feature of described organic sulfur positive electrode material also is to have sulphur one sulfide linkage when Charging state, and this key ruptures when battery discharge and forms organic sulfur metal salt with metal ion in the above-mentioned battery; And
(c) between described anode and negative electrode, can between described anode and negative electrode, carry out the electrolyte release agent that ion transmitted and contained organic polymer and electrolytic salt.
2, the battery of claim 1, wherein said solid metal anode comprises a metal that is selected from alkali metal and alkaline-earth metal.
3, the battery of claim 1, wherein said solid metal anode comprises a metal that is selected from lithium and sodium.
4, the battery of claim 1, wherein said solid metal anode comprises lithium.
5, the battery of claim 1, wherein said solid metal anode comprises sodium.
6, the battery of claim 1, wherein said SOLID ORGANIC sulphur negative electrode also comprises 0-20%(weight) conductive particles.
7, the battery of claim 6, wherein said SOLID ORGANIC sulphur negative electrode comprises 0-10%(weight) carbon granule.
8, the battery of claim 6, wherein said SOLID ORGANIC sulphur anode comprises 0-70%(weight) polymer dielectric.
9, the battery of claim 8, wherein said SOLID ORGANIC sulphur anode comprises 0-70%(weight) polyoxyalkylene polymers.
10, the battery of claim 1, wherein said SOLID ORGANIC sulphur negative electrode comprises:
(a) conductive particle about 1-20%(weight);
(b) polymer dielectric about 20-70%(weight); And
(c) at Charging state, remaining is basically by described formula (R(S) y) organic sulfur polymer of n forms.
11, the battery of claim 1, wherein the described organic polymer in the described electrolyte release agent between described anode and negative electrode is selected from polyethers, poly-imines, poly-sulfo-ether, polyphosphazene.
12, the battery of claim 1, wherein the described organic polymer in the described electrolyte release agent between described anode and negative electrode comprises polyoxyalkylene.
13, the battery of claim 12, wherein said organic polymer comprises the polyoxygenated ethylidene.
14, the battery of claim 1, wherein the described electrolytic salt in the described electrolyte release agent between described anode and negative electrode comprises lithium triflate.
15, a kind of solid metallic sulphur battery, it comprises:
(a) solid lithium anode;
(b) SOLID ORGANIC sulphur negative electrode, it comprises (at a Charging state) formula (R(S) y) polymer of n, Y=2-6 wherein, n is greater than 20, R is one or more identical or different aliphatic series with 1-20 carbon atom or aromatics part, when comprising one or more aromatic ring, R may contain one or more oxygen, sulphur or nitrogen heteroatom, when comprising aliphatic chain, R may contain one or more oxygen that associate with this chain, sulphur, nitrogen or fluorine atom, wherein aliphatic group can be a straight or branched, saturated or unsaturated, wherein may have substituting group on aliphatic chain or the aromatic ring, the feature of described organic sulfur positive electrode material also is to have sulphur-sulfide linkage when Charging state, and this key ruptures when battery discharge and forms organic sulfur metal salt with metal ion in the described battery.
(c) between described anode and negative electrode, can between described anode and negative electrode, carry out the electrolyte release agent that ion transmitted and contained organic polymer and electrolytic salt.
16, a kind of solid metallic sulphur battery, it comprises:
(a) solid lithium anode;
(b) SOLID ORGANIC sulphur negative electrode, it comprises (at a Charging state) formula (R(S) y) n) polymer, it is Y=2-6, n is greater than 20, R is one or more identical or different aliphatic series with 1-20 carbon atom or aromatics part, when comprising one or more aromatic ring, R may contain one or more oxygen, sulphur or nitrogen heteroatom, when R comprises aliphatic chain, may contain one or more and oxygen this association, sulphur, nitrogen or fluorine atom, wherein aliphatic group can be a straight or branched, saturated or unsaturated, wherein may have substituting group on aliphatic chain or the aromatic ring, the feature of described organic sulfur positive electrode material also is to have sulphur-sulfide linkage when Charging state, and this key ruptures when battery discharge and forms organic sulfur metal salt with metal ion in the described battery.
(c) between described anode and negative electrode, can between described anode and negative electrode, carry out the electrolyte release agent that ion transmitted and contained organic polymer and electrolytic salt, described organic polymer is selected from polyethers, poly-imines, poly-sulfo-ether, polyphosphazene and composition thereof.
17, a kind of solid metallic sulphur battery, it comprises:
(a) solid lithium anode;
(b) SOLID ORGANIC sulphur negative electrode, it comprises (at a Charging state) formula (R(S) y) polymer of n, Y=2-6 wherein, n is greater than 20, R is one or more identical or different aliphatic series with 1-20 carbon atom or aromatics part, when comprising one or more aromatic ring, R may contain one or more oxygen, sulphur or nitrogen heteroatom, when comprising aliphatic chain, R may contain one or more oxygen that associate with this chain, sulphur, nitrogen or fluorine atom, wherein aliphatic group can be a straight or branched, saturated or unsaturated, wherein may have substituting group on aliphatic chain or the aromatic ring, the feature of described organic sulfur positive electrode material also is to have sulphur-sulfide linkage when Charging state, and this key ruptures when battery discharge and forms organic sulfur metal salt with metal ion in the described battery.
(c) between described anode and negative electrode, can between described anode and negative electrode, carry out the electrolyte release agent that ion transmitted and contained one or more polyether polymers and a kind of electrolytic salt.
18, the battery of claim 17, wherein the described polyether polymer in the described electrolyte release agent between described anode and negative electrode comprises polyoxyalkylene.
19, the battery of claim 17, wherein the described electrolytic salt in the described electrolyte release agent between described anode and negative electrode comprises lithium triflate.
20, the battery of claim 17, wherein said SOLID ORGANIC sulphur negative electrode comprises:
(a) conductive particle about 1-20%(weight);
(b) polymer dielectric about 20-70%(weight); And
(c) at Charging state, remaining is basically by described formula (R(S) y) organic sulfur polymer of n forms.
CN90109212A 1989-10-13 1990-10-13 Cell for making secondary batteries Expired - Fee Related CN1023364C (en)

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