Patent Application
20210020979
According to the invention, an electrolyte for an alkali-sulfur battery is provided. In addition, an alkali-sulfur battery which comprises the electrolyte according to the invention is presented. The electrolyte according to the invention comprises a mixture of a sulphone and a fluorine-containing ether in a volume ratio of ≥1:4 (v:v). By using this electrolyte, the shuttling of polysulphide species from the cathode to the anode can be effectively suppressed even without the use of LiNO3. Even without the use of LiNO3, a high coulomb efficiency, long-term stability (low self-discharge) and cyclability is achieved by the electrolyte in alkali-sulfur batteries. Coulomb efficiency, long-term stability and cyclability could also be improved further by the use of a cathode which comprises an additive for homogenised distribution of polysulphide within the cathode. In addition, uses of components of the alkali-sulfur battery according to the invention are proposed.
In lithium-sulfur batteries, occurs formation of so-called lithium-polysulphides (Li2Sn, 2≤n≤8). Some of these polysulphide species are soluble in the commonly used electrolytes (e.g. a mixture of DME:DOL with a conductive salt). The dissolved polysulphides can penetrate the separator and are reduced to form lower polysulphide species on the anode. During the charging process, reoxidation on the cathode follows the reduction, as a result of which a circulation process which significantly reduces the coulomb efficiency of the accumulator results. If the battery is stored in the charged state, the result can likewise be formation of soluble polysulphides which are reduced on the anode. As a result, the capacity of the cell is reduced. Furthermore, the cyclability is reduced due to irreversible processes associated with these processes.
It is known in the state of the art that the addition of N—O-containing compounds (such as e.g. LiNO3) leads to a substantially improved coulomb efficiency and cyclability. This mechanism begins on the lithium anode. It is assumed that, as a result of the nitrate compounds, the result is formation of sulphitic species on the surface of the lithium anode.
The addition of LiNO3 or other N—O-containing compounds does not however solve the problem comprehensively. Firstly, degradation of the anode cannot be completely prevented by the presence of LiNO3. In addition, the protective effect on the anode side decreases continuously, since continual repair processes on the surface film of the anode consume LiNO3 and also active material in the form of polysulphide species. Consequently, this has a negative effect on the cyclability of the cell. Furthermore, LiNO3 influences the chemistry of the cell negatively as a result of subsidiary reactions. Hence the requirement exists in the state of the art for solutions which are successful without the use of LiNO3.
Polyethylene oxide-based polymer electrolytes have been used successfully already as cathode supplement or as membrane in lithium-sulfur batteries but cannot, per se, completely suppress the polysulphide shuttle.
Fluorine-containing ethers (in particular TTE or HFE) have been used in the past as electrolyte additive, these being distinguished by low solubility for polysulphides. However complete suppression of the polysulphide shuttle could not be achieved even with fluorine-containing ethers as electrolyte additive. In an attempt at improvement, LiNO3 was added to the electrolyte, which led however to the occurrence of high excess potentials which imply kinetic restriction of the polysulphide conversion. A further disadvantage is that only low use of the active material (<70%) is possible.
Starting herefrom, it was the object of the present invention to provide an electrolyte for an alkali-sulfur battery which, even without use of LiNO3, effects improved suppression of the polysulphide shuttle and hence ensures high coulomb efficiency, long-term stability (low self-discharge) and cyclability in alkali-sulfur batteries.
The object is achieved by the electrolyte and the alkali-sulfur battery described herein and the advantageous developments thereof. Uses according to the invention are also described.
According to the invention, an electrolyte for an alkali-sulfur battery is provided, the electrolyte comprising a sulphone and a fluorine-containing ether or consisting thereof and being characterised in that the volume ratio of the sulphone to the fluorine-containing ether is 1:4 (v:v). The electrolyte according to the invention comprises a sulphone, which effects particularly high oxidation stability. In addition, the electrolyte has increased reliability relative to inflammability and hence permits the use in alkali-sulfur batteries over a wide temperature range. Furthermore, the electrolyte effects a high coulomb efficiency, long-term stability (low self-discharge) and cyclability in alkali-sulfur batteries.
In the electrolyte according to the invention, the volume ratio of the sulphone to the fluorine-containing ether is preferably 1:3 (v:v), particularly preferably 1:3 (v:v) to 1:1 (v:v).
The electrolyte can be liquid, gel-like or solid, preferably liquid or gel-like, particularly preferably liquid. The indicated aggregate states relate to room temperature (25° C.).
The fluorine-containing ether can be selected from the group consisting of 2,2,2-trifluoroethylmethylether, 2,2,2-trifluoroethyldifluoromethylether, 2,2,3,3,3-pentafluoropropylmethylether, 2,2,3,3,3-pentafluoropropyldifluoromethylether, 2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethylether, 1,1,2,2-tetrafluoroethylmethylether, 1,1,2,2-tetrafluoroethylethylether, 1,1,2,2-tetrafluoroethylpropylether, 1,1,2,2-tetrafluoroethylbutylether, 1,1,2,2-tetrafluoroethylisobutylether, 1,1,2,2-tetrafluoroethylisopentylether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethylether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether, hexafluoroisopropylmethylether, 1,1,3,3,3-pentafluoro-2-trifluoromethylpropylmethylether, 1,1,2,3,3,3-hexafluoropropylmethylether, 1,1,2,3,3,3-hexafluoropropylethylether, and 2,2,3,4,4,4-hexafluorobutyldifluoromethylether, preferably 1,1,2,2-tetrafluoroethylpropylether, particularly preferably 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether.
The sulphone can be selected from the group consisting of non-cyclic aliphatic sulphones (preferably ethylmethylsulphone, ethylvinylsuphone and/or butylsulphone) and cyclic aliphatic sulphones (preferably tetramethylene sulphone). Optionally, the sulphone is a fluorinated sulphone or not a fluorinated sulphone. Non-fluorine-containing sulphones, such as e.g. sulpholane, have a positive effect both on the cathode chemistry and on the anode surface since they have particularly high oxidation stability and also good compatibility with lithium.
The electrolyte can comprise a salt which is selected from the group consisting of LiPF6, LiBF4, LiClO4, LiSO3CF3, LiN(SO2F)2, LiN(SO2CF3)2, LiN(SO2F)(SO2CF3), LiN(SO2F)(SO2C4F9), LiN(SO2CF2CF3)2, LiC(SO2CF2CF3)3, LiC(SO2CF3)3, LiI, LiCl, LiF, LiPF5(SO2CF3), LiPF4(SO2CF3)2, and mixtures hereof, preferably LiN(SO2CF3)2. The salt is preferably contained in a concentration of >0 mol/l to ≤2.5 mol/l.
In a further preferred embodiment, the electrolyte comprises no LiNO3.
Furthermore, an alkali-sulfur battery is provided according to the invention, comprising
The alkali-sulfur battery is distinguished by high coulomb efficiency, long-term stability (low self-discharge) and cyclability.
The alkali-sulfur battery can be characterised in that the cathode comprises 40 to 80% by weight, preferably 50 to 70% by weight, particularly preferably 55 to 65% by weight, of sulfur, relative to the total weight of the cathode. Furthermore, the cathode can comprise 20 to 50% by weight, preferably 25 to 45% by weight, particularly preferably 30 to 40% by weight, of carbon, relative to the total weight of the cathode.
In addition, the cathode can comprise 1 to 30% by weight, preferably 2 to 20% by weight, particularly preferably 2.5 to 15% by weight, of additive for homogenised distribution of polysulphide within the cathode, relative to the total weight of the cathode. Because of the low solubility of polysulphides in the electrolyte according to the invention, the reactivity thereof in the cathode is generally low. The additive increases locally, in the cathode, the solubility and distribution of polysulphides and alkali sulphides (e.g. Li2S) and hence ensures high reactivity of polysulphides and the reversibility of conversion thereof during battery operation. It is advantageous if the additive is contained only in the cathode of the alkali-sulfur battery, i.e. not in the separator and electrolyte. If the additive were present e.g. also in the separator or distributed homogeneously in the electrolyte, the polysulphide shuttling would be assisted and the coulomb efficiency would be impaired. Local limitation of the additive to the cathode can be achieved for example by the additive being present as a gel or being bonded chemically covalently to the cathode.
The additive for homogenised distribution of polysulphide can comprise a redox mediator for alkali polysulphide, preferably a redox mediator for lithium polysulphide, particularly preferably a metal oxide as redox mediator for lithium polysulphide, in particular manganese oxide, aluminium oxide and/or titanium oxide, or can consist thereof.
Furthermore, the additive for homogenised distribution of polysulphide can comprise a polymer, which polymer comprises oxygen atoms, nitrogen atoms and/or halogen atoms or consist thereof, preferably a polymer which comprises the ether functionality —(CH2—CH2—O—)n with n≥1, particularly preferably polyethylene oxide. This polymer (e.g. PEO) has the effect that (short-chain) polysulphide species are brought or kept in solution in situ on the cathode side and hence a locally increased stabilisation and conversion of these polysulphide species takes place without these being able to move from the cathode side to the anode side. Therefore good kinetics for the conversion of active material is achieved, the shuttle mechanism being effectively suppressed even without use of LiNO3. The anode is therefore not contacted by polysulphide species but merely by the (e.g. liquid) electrolyte, the degradation products of which form a stable, insoluble surface film. Furthermore, it was observed that, by means of the polymer, a significantly higher active material use of almost 90% is possible (without the polymer only approx. 70%) and a surprisingly long discharge plateau between 1.8-2.0 V occurs.
Preferably, the cathode comprises a gel or consists thereof. The gel state of the cathode can occur for example by the cathode comprising a specific concentration of the above-mentioned polymer (e.g. PEO). Insoluble cathode components (e.g. carbon and/or sulfur) are preferably wetted by the above-mentioned polymer.
The cathode can comprise a binder, the binder being selected preferably from the group consisting of styrene-butadiene rubber, polytetrafluoroethylene, gelatines, polyacrylic acid, carboxymethyl cellulose, polyvinylpyrrolidone and polyvinylidene fluoride, particularly preferably styrene-butadiene rubber and polytetrafluoroethylene. The binder can be contained in a concentration of 1 to 10% by weight, preferably 1.5 to 8% by weight, particularly preferably 2 to 6% by weight, relative to the total weight of the cathode.
Preferably, the cathode comprises amorphous carbon, carbon nanotubes and/or carbon nanofibres, the amorphous carbon being particularly preferably carbon black. Furthermore, the cathode can comprise amorphous carbon and carbon nanofibres, the weight ratio of amorphous carbon to carbon nanofibres being preferably from 5:1 (w:w) to 20:1 (w:w), preferably from 8:1 (w:w) to 16:1 (w:w), particularly preferably from 10:1 (w:w) to 12:1 (w:w).
The amorphous carbon preferably has pores, particularly preferably micropores and mesopores, in particular micropores with a diameter of >0 to 2 nm and mesopores with a diameter of 2 to 50 nm.
In a preferred embodiment, the sulfur-containing cathode active material is distributed homogeneously in the carbon of the cathode. Preferably, the sulfur-containing cathode active material is present in pores of the carbon, particularly preferably in pores of the amorphous carbon, the cathode active material being present in particular melted in the pores.
In a preferred embodiment, the cathode comprises an inorganic solid which does not concern sulfur, preferably a redox mediator for alkali polysulphide, particularly a redox mediator for lithium polysulphide, in particular manganese dioxide, aluminium oxide and/or titanium oxide (optionally in so-called nanosheets).
The separator can comprise polypropylene or consist thereof.
The use of a composition comprising or consisting of a fluorine-containing ether and a sulphone, preferably 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether and tetramethylene sulphone (sulpholane), as electrolyte in alkali-sulfur batteries, preferably lithium-sulfur batteries, is proposed.
Furthermore the use of a composition comprising or consisting of polyethylene oxide, preferably polyethylene oxide and styrene-butadiene rubber, particularly preferably polyethylene oxide, styrene-butadiene rubber and polyvinylpyrrolidone, as binder for cathodes in alkali-sulfur batteries, preferably lithium-sulfur batteries, is proposed.
The subject according to the invention is intended to be explained in more detail with reference to the subsequent Figures and examples without wishing to restrict said subject to the specific embodiments represented here.
An alkali-sulfur battery according to the invention can be produced by a method which comprises the following steps
In the method, step a) can be implemented at a temperature of 100 to 200° C., preferably 130 to 170° C., for 10 minutes to 60 minutes, preferably 20 minutes to 40 minutes. In step b) and/or step d), grinding takes place in an oscillating mill. In step f), firstly drying takes place at 20 to 30° C. and subsequently the layers are heated for 1 to 2 hours at 80° C.
For production of the cathode, firstly a KB/S composite (8:15, m:m) is produced by melting of carbon black (Ketjen black EC600-JD=KB) and sulfur (S) in a drying cabinet at 155° C. for 12 h.
Subsequently, mixing-in of a slurry made of
The binder was hereby used as 4% (% by weight) solution in H2O, after which KB/S composite+CNF was ground at 25 Hz for 10 min in an oscillating mill (Retsch MM400). Furthermore, also 5 ml H2O was added to the slurry. Subsequently, a second grinding process followed at 25 Hz for 30 min.
A layer is knife-coated, which layer is dried overnight at room temperature and subsequently at 80° C. for 1.5 h in air and subsequently calendered. The sulfur loading of the layer (active layer) was approx. 1.4 mg sulfur/cm2 and the density thereof approx. 0.7 g/cm3 and can be used as cathode in alkali-sulfur batteries.
The cathode obtained by the above-mentioned method was subsequently built up in a button cell (CR2016). The components were:
In the button cell, an electrolyte was used, which comprises 1 M LiTFSI (Aldrich, 99.95%) and 0.25 M LiNO3 (Alfa Aesar, 99.98%, water-free) in
(=reference electrolyte). The electrolyte-to-sulfur ratio was 8 μl electrolyte/mg sulfur.
The cell was subsequently measured galvanostatically, the cycling (charge/discharge being effected at a rate of C/10 between 1.8-2.6 V vs. Li/Li+. The result is illustrated in
The cathode comprising PEO-additive of Example 2 was built up in the same button cell as in Example 2.
In the button cell, an electrolyte was however used, which comprises 1 M LiTFSI (Aldrich, 99.95%) in
The electrolyte-to-sulfur ratio was 8 μl electrolyte/mg sulfur.
The cell was subsequently measured galvanostatically, the cycling (charge/discharge) being effected at a rate of C/10 between 1.5-2.6 V vs. Li/Li+. In the 1st cycle for forming the cell, the discharge was effected at a rate of C/10 up to 1.0 V vs. Li/Li+. The result is illustrated in
The cathode comprising PEO-additive of Example 2 was built up in the same button cell as in Example 2.
As electrolyte of the button cell, an electrolyte was however used, which comprises 1 M LiTFSI (Aldrich, 99.95%) in
The electrolyte-to-sulfur ratio was 8 μl electrolyte/mg sulfur.
The cell was subsequently measured galvanostatically, the cycling (charge/discharge) being effected at a rate of C/10 between 1.5-2.6 V vs. Li/Li+. In the 1st cycle for forming the cell, the discharge was effected at a rate of C/10 to 1.0 V vs. Li/Li+. The result is illustrated in
The cathode comprising PEO-additive of Example 2 was built up in the same button cell as in Example 2.
As electrolyte of the button cell, an electrolyte was however used, which comprises 0.8 M LiTFSI (Aldrich, 99.95%) in
The electrolyte-to-sulfur ratio was 8 μl electrolyte/mg sulfur.
The cell was subsequently measured galvanostatically, the cycling (charge/discharge) being effected at a rate of C/10 between 1.5-2.6 V vs. Li/Li+. In the 1st cycle for forming the cell, the discharge was effected at a rate of C/10 to 1.0 V vs. Li/Li+. The result is illustrated in
Firstly, a KB/S composite (1:2, m:m) was produced by melting of carbon black (Ketjen black EC600-JD=KB) and sulfur (S) in a drying cabinet at 155° C. for 12 h.
Subsequently, KB/S (97%) was ground with PTFE binder (3%) at increased temperature and pressed dry by a rolling process to form a cathode film.
Subsequently, lamination was effected on carbon-primed aluminium foil. The sulfur loading of the active layer was approx. 2.2 mg sulfur/cm2 and the density thereof approx. 0.6 g/cm3.
The obtained cathode without additive was built up in the same button cell as in Example 2.
As electrolyte of the button cell, an electrolyte was however used, which comprises 1.0 M LiTFSI (Aldrich, 99.95%) in
The electrolyte-to-sulfur ratio was 8 μl electrolyte/mg sulfur.
The cell was subsequently measured galvanostatically, the cycling (charge/discharge) being effected at a rate of C/10 between 1.5-2.6 V vs. Li/Li+. In the 1st cycle for forming the cell, the discharge was effected at a rate of C/10 up to 1.0 V vs. Li/Li+. The result is illustrated in
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2015 208 197.4 | May 2015 | DE | national |
This patent application is a divisional of U.S. patent application Ser. No. 15/570,818, filed on Oct. 31, 2017, which is the U.S. national phase of International Application No. PCT/EP2016/059397, filed on Apr. 27, 2016, which claims the benefit of German Patent Application No. 10 2015 208 197.4, filed May 4, 2015, the disclosures of which are incorporated herein by reference in their entireties for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15570818 | Oct 2017 | US |
| Child | 17037466 | US |
