Sulfide-impregnated solid-state battery
11539071 · 2022-12-27
Assignee
Inventors
- Zhe LI (Shanghai, CN)
- Xiaochao Que (Shanghai, CN)
- Haijing LIU (Shanghai, CN)
- Yong LU (Shanghai, CN)
- Mark W. Verbrugge (Troy, MI, US)
- Meiyuan WU (Shanghai, CN)
Cpc classification
H01M4/13
ELECTRICITY
H01M10/0585
ELECTRICITY
H01M4/62
ELECTRICITY
Y02E60/10
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
Y02P70/50
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
H01M10/056
ELECTRICITY
H01M2300/0045
ELECTRICITY
H01M10/0525
ELECTRICITY
International classification
Abstract
A sulfide-impregnated solid-state battery is provided. The battery comprises a cell core constructed by basic cell units. Each unit comprises a positive electrode comprising a cathode layer and a positive meshed current collector comprising a conductive material which is further coated by oxide-based solid-state electrolyte. The cell unit further comprises a negative electrode comprising an anode layer and a negative meshed current collector comprising a conductive material which is further coated by oxide-based solid-state electrolyte. The positive and negative electrodes are stacked together to form the cell unit. The two coated oxide-based solid electrolyte layers are disposed between the positive and negative electrode as dual separators. Such a cell unit may be repeated or connected in parallel or bipolar stacking to form the cell core to achieve a desired battery voltage, power and energy. The cell core comprises a sulfide-based solid-state electrolyte dispersed in the pore structures of cell core.
Claims
1. A sulfide-impregnated solid-state battery comprising: a cell core constructed by cell units and having a pore structure, each cell unit comprising: a positive electrode comprising a cathode layer and a positive meshed current collector comprising a conductive material, wherein the cathode layer is further coated by an oxide-based solid electrolyte layer; and a negative electrode comprising an anode layer and a negative meshed current collector comprising a conductive material, wherein the anode layer is further coated by an oxide-based solid electrolyte layer, wherein the positive electrode and the negative electrode are stacked together to form the cell unit, and the two of the coated oxide-based solid-state electrolyte layers are disposed between the positive electrode and the negative electrode as dual separators, wherein the cathode layer comprises between about 30 wt % and about 98 wt % cathode active material, between about 0 wt % and about 50 wt % sulfide-based solid-state electrolyte, between about 0 wt % and about 30 wt % conductive additive, and between about 0 wt % and about 20 wt % binder, wherein the anode layer comprises between about 30 wt % and about 98 wt % anode active material, between about 0 wt % and about 50 wt % sulfide-based solid-state electrolyte, between about 0 wt % and about 30 wt % conductive additive, and between about 0 wt % and about 20 wt % binder, and wherein a sulfide-base solid-state electrolyte is dispersed in the pore structure of the cell core.
2. The battery of claim 1 wherein each cell unit is connected in one of parallel arrangement and bipolar arrangement.
3. The battery of claim 1 wherein the cathode active material is selected from the group consisting of a high-voltage cathode material, a rock salt layered oxide, a spinel, a polyanion cathode, a lithium transition-metal oxide, and at least one of LiNi.sub.0.5Mn.sub.1.5O.sub.4, LiNbO.sub.3-coated LiNi.sub.0.5Mn.sub.1.5O.sub.4, LiCoO.sub.2, LiNi.sub.xMn.sub.yCo.sub.1-x-yO.sub.2, LiNi.sub.xMn.sub.1-xO.sub.2, Li.sub.1+xMO.sub.2, LiMn.sub.2O.sub.4, LiV.sub.2(PO.sub.4).sub.3.
4. The battery of claim 1 wherein the anode active material is selected from the group consisting of a carbonaceous material, silicon, silicon-graphite mixture, Li.sub.4Ti.sub.5O.sub.12, transition-metal, metal oxide, and sulfide.
5. The battery of claim 1 wherein each of the cathode layer and the anode layer has a thickness of between about 1 micrometer and about 1000 micrometers.
6. The battery of claim 1 wherein each of the positive meshed current collector and the negative meshed current collector has a thickness of between about 4 micrometers and about 200 micrometers and a pore size of between about 50 nm and 2000 um.
7. The battery of claim 1 wherein the positive meshed current collector and the negative meshed current collector is selected from the group consisting of aluminum, nickel, iron, titanium, copper, tin, and alloys thereof.
8. The battery of claim 1 wherein the positive meshed current collector and the negative meshed current collector includes flat foils of conductive material with no holes.
9. The battery of claim 1 wherein the oxide-based solid electrolyte layers disposed on the cathode layer and anode layer comprise an oxide-based solid-state electrolyte of Li.sub.3xLa.sub.2/3-xTiO.sub.3, Li.sub.1.4Al.sub.0.4Ti.sub.1.6(PO.sub.4).sub.3 and Li.sub.1+xAl.sub.xGe.sub.2-x(PO.sub.4).sub.3, Li.sub.2+2xZn.sub.1-xGeO.sub.4, Li.sub.7La.sub.3Zr.sub.2O.sub.12 or mixtures thereof.
10. The battery of claim 1 wherein the oxide-based solid electrolyte layers disposed on the cathode layer and anode layer comprise at least one of a metal-doped and aliovalent-substituted oxide-based solid-state electrolyte, a borate and a phosphate solid-state electrolyte, and an oxide ceramic powder.
11. The battery of claim 1 wherein the oxide-based solid electrolyte layers disposed on the cathode layer and anode layer comprise same or different chemical compositions.
12. The battery of claim 1 wherein the oxide-based solid electrolyte layers disposed on the cathode layer and anode layer each have a thickness of between about 50 nanometers and about 1000 micrometers.
13. The battery of claim 1 wherein the sulfide-base solid-state electrolyte comprises at least one of a pseudobinary sulfide, a pseudoternary sulfide, and a pseudoquaternary sulfide, wherein the pseudobinary sulfide comprises one of Li.sub.3PS.sub.4, Li.sub.7P.sub.3S.sub.11, Li.sub.4SnS.sub.4, and 80Li.sub.2S.20P.sub.2S.sub.5, wherein the pseudoternary sulfide comprises one of Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4, Li.sub.6PS.sub.5Br, Li.sub.6PS.sub.5I, Li.sub.6PS.sub.5Cl, Li.sub.7P.sub.2S.sub.8I, Li.sub.4PS.sub.4I, and LiI—Li.sub.4SnS.sub.4, and wherein the pseudoquaternary sulfide comprises one of Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3 and Li.sub.10.35[Sn.sub.0.27Si.sub.1.08]P.sub.1.65S.sub.12.
14. The battery of claim 1 wherein the cell core further includes a liquid electrolyte selected from the group consisting of Li(triethylene glycol dimethyl ether)bis(trifluoromethanesulfonyl)imide (Li(G.sub.3)TFSI), LiPF6-EC/DEC with additives, and LiTFSI in acetonitrile.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
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DETAILED DESCRIPTION
(15) The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
(16) Referring to
(17) As shown in
(18) In one embodiment, the conductive additive of the cathode layer may comprise any suitable material such as carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes and other electronically conductive additives. Moreover, the binder of the cathode layer may comprise poly(tetrafluoroethylene) (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile butadiene rubber (NBR), styrene ethylene butylene styrene copolymer (SEBS), styrene butadiene styrene copolymer (SBS).
(19) Moreover, cathode layer 18 may have a thickness of between about 1 micrometer and about 1000 micrometers. In this embodiment, the positive meshed current collector 20 comprises a conductive material and has a thickness of between about 4 micrometers and about 200 micrometers. The conductive material may comprise aluminum, nickel, iron, titanium, copper, tin, and alloys thereof. Moreover, the meshed current collector has a pore size of between about 50 nm and 2000 um. In yet another aspect, all/part of the positive meshed current collectors could also be replaced by the flat foils of conductive material with no meshes (holes).
(20) As shown in
(21) In this embodiment, the anode active material may comprise carbonaceous material (for example, graphite, hard carbon, and soft carbon), silicon, silicon-graphite mixture, Li.sub.4Ti.sub.5O.sub.12, transition-metal (for example, Sn), metal oxide or sulfide (for example, TiO.sub.2, FeS), and other lithium-accepting anode materials.
(22) In one embodiment, the conductive additive of the anode layer may comprise any suitable material such as carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, carbon nanotubes and other electronically conductive additives. Moreover, the binder of the anode layer may comprise poly(tetrafluoroethylene) (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile butadiene rubber (NBR), styrene ethylene butylene styrene copolymer (SEBS), styrene butadiene styrene copolymer (SBS).
(23) Preferably, the negative meshed current collector has a thickness of between about 4 micrometers and about 200 micrometers. Moreover, the negative meshed current collector has a pore size of between about 50 nm and 2000 um. In yet another aspect, all/part of the negative meshed current collectors could also be replaced by the flat foils of conductive material with no meshes (holes).
(24) The positive electrode 16 and the negative electrode 22 are staked in parallel and separated by a first coated separator layer 28 comprised of oxide-based solid electrolyte and a second coated separator layer 29 comprised of oxide-based solid electrolyte. As shown, first separator layer 28 is directly coated onto positive electrode 16 and second separator layer 29 is directly coated onto negative electrode layer 22. Preferably, the coated separator layer has a thickness of between about 50 nanometers and about 1000 micrometers.
(25) In one embodiment, the coated separator layers 28,29 may comprise at least one of an oxide-based solid-state electrolyte, metal-doped and aliovalent-substituted oxide-based solid-state electrolytes. For example, the coated separator layer may comprise one of an Li.sub.7La.sub.3Zr.sub.2O.sub.12, aluminum-doped Li.sub.7La.sub.3Zr.sub.2O.sub.12, Sb-doped Li.sub.7La.sub.3Zr.sub.2O.sub.12 Ga-substituted Li.sub.7La.sub.3Zr.sub.2O.sub.12, a Cr and V-substituted LiSn.sub.2P.sub.3O.sub.12, and an Al-substituted perovskite. In another embodiment, the coated separator layers may comprise one of a borate or phosphate solid-state electrolyte, e.g., Li.sub.2B.sub.4O.sub.7, Li.sub.3PO.sub.4, LiPON (Li.sub.2.88PO.sub.3.73N.sub.0.14) and Li.sub.2O—B.sub.2O.sub.3—P.sub.2O. In yet another example, the coated separator layers may comprise a dry air-stable solid-state electrolyte. e.g., Li.sub.3.833Sn.sub.0.833As.sub.0.166S.sub.4, LiI—Li.sub.4SnS.sub.4, and Li.sub.4SnS.sub.4. The coated separator layer may also comprise an oxide ceramic powder, e.g., SiO.sub.2, CeO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2.
(26) In this embodiment, each of the current collectors have tabs extending from the top sides of electrodes. As shown in
(27) As shown in
(28) In one example, the S-SSE precursor solution comprises a Li.sub.6PS.sub.5Cl-ethanol solution. In another example, the S-SSE precursor solution comprises at least one of a pseudobinary sulfide with solvent, a pseudoternary sulfide with solvent, and a pseudoquaternary sulfide with solvent. In this aspect, the pseudobinary sulfide comprises one of Li.sub.3PS.sub.4, Li.sub.7P.sub.3S.sub.11, Li.sub.4SnS.sub.4, and 80Li.sub.2S.20P.sub.2S.sub.5. The pseudoternary sulfide may comprise one of Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4, Li.sub.6PS.sub.5Br, Li.sub.6PS.sub.5Cl, Li.sub.7P.sub.2S.sub.8I, LI.sub.4PS.sub.4I, and LiI—Li.sub.4SnS.sub.4. Further, the pseudoquaternary sulfide may comprise one of Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3 and Li.sub.10.35[Sn.sub.0.27Si.sub.1.08]P.sub.1.65S.sub.12. In this example, the solvent may comprise at least one of a tetrahydrofuran, ethyl propionate, ethylacetate, acetonitrile, water, N-methyl formamide, methanol, ethanol, ethanol-tetrahydrofuran co-solvent and 1,2-dimethoxyethane. In another example, the S-SSE precursor solution comprises Li.sub.10GeP.sub.2S.sub.12, a polyethylene oxide and an acetonitrile solvent. In some examples, to improve the S-SSE dispersibility, some dispersant (such as Triton X-100) are further added into S-SSE precursor solution
(29) As depicted in
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(31) As depicted in
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(33) Furthermore, method 10 further comprises a step 40 of fully sealing the cell core. In this example, cell core 14 may be fully sealed into any suitable manner. For example, the cell core may be fully sealed by way of vacuum seal thereby minimizing exposure to air. Thus, the cell core may be placed in an aluminum laminated bag, can or container, and followed by fully vacuum sealing.
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(35) In one embodiment, the pseudobinary sulfide may comprise one of Li.sub.3PS.sub.4, Li.sub.7P.sub.3S.sub.11, Li.sub.4SnS.sub.4, and 80Li.sub.2S.20P.sub.2S.sub.5. In another embodiment, the pseudoternary sulfide may comprise one of Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4, Li.sub.6PS.sub.5Br, Li.sub.6PS.sub.5I, Li.sub.6PS.sub.5Cl, Li.sub.7P.sub.2S.sub.8I, Li.sub.4PS.sub.4I, and LiI—Li.sub.4SnS.sub.4. In yet another embodiment, the pseudoquaternary sulfide may comprise one of Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3 and Li.sub.10.35[Sn.sub.0.27Si.sub.1.08]P.sub.1.65S.sub.12.
(36) It should be understood that cell unit (same as the one in cell core 14 of
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(39) The description of the present disclosure is merely exemplary in nature and variations that do not depart from the gist of the present disclosure are intended to be within the scope of the present disclosure. Such variations are not to be regarded as a departure from the spirit and scope of the present disclosure.