CN217035901U - Internal series solid-state battery and solid-state battery pack - Google Patents
Internal series solid-state battery and solid-state battery pack Download PDFInfo
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- CN217035901U CN217035901U CN202220117266.4U CN202220117266U CN217035901U CN 217035901 U CN217035901 U CN 217035901U CN 202220117266 U CN202220117266 U CN 202220117266U CN 217035901 U CN217035901 U CN 217035901U
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- 239000007784 solid electrolyte Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 13
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 3
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical group [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 claims 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 25
- 239000007773 negative electrode material Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005056 compaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Cell Electrode Carriers And Collectors (AREA)
Abstract
The utility model discloses an internal series solid-state battery, which comprises two or more battery units, wherein each battery unit comprises a current collector, a solid electrolyte layer and an electrode layer formed by a positive electrode layer and a negative electrode layer; the two or more battery units form a series-connection type solid-state battery in a superposition mode, and two adjacent battery units are superposed to enable a current collector of one battery unit to contact an electrode layer of the other battery unit; the current collector is an aluminum current collector, and the negative electrode layer is a niobium oxide layer. Solid state batteries made therefrom are also disclosed. According to the internal series solid-state battery, the niobium oxide is used as the negative electrode material, so that the aluminum foil can be used as the bipolar current collector, and the defect that the composite foil is difficult to process when used as the bipolar current collector in the prior art is overcome.
Description
Technical Field
The present invention relates to the field of solid-state batteries, and particularly to an internal series solid-state battery and a solid-state battery pack.
Background
In the existing energy storage technology, a lithium ion battery is widely applied to the fields of new energy automobiles and the like by virtue of the advantages of high energy density, high working voltage, long service life, no memory effect and the like. However, the traditional lithium ion battery adopts flammable liquid organic electrolyte, so that potential safety hazards exist, and development encounters a bottleneck. The all-solid-state lithium battery obtained by using the solid electrolyte to replace the organic liquid electrolyte has good safety, has larger space in the aspects of improving specific energy, specific power density and cycle performance, and is expected to become a next-generation lithium ion battery.
In the solid-state battery, the internal series connection is the unique advantage of the solid-state battery, and means that the bipolar electrodes are formed by coating active materials of lithium ion batteries with different polarities on two sides of a current collector, and the internal structure series connection is realized through superposition, so that the high-voltage battery is obtained. The battery has the characteristics of high energy density and strong overcurrent capacity. However, in order to produce such an internal series type solid-state battery, a bipolar current collector is required, and the current collector must be resistant to oxidation and reduction. And it must also ensure that the cell is electronically conductive while the current collector is internally insulated, and that electrolyte does not penetrate in the middle, otherwise it will short circuit from the inside.
At present, aluminum foil and copper foil commonly used in current collectors cannot meet the requirements of bipolar current collectors, and enterprises generally compound metal foils directly together to form a compound foil or bond the metal foils to two sides of a polymer layer with viscosity (for example, patent publications CN108390068A, CN103219521A and CN 102668225A). However, since metal foils are generally formed by rolling, the thickness cannot be made very thin, and even if the metal foils are made very thin, the number of the surfaces thereof increases, and micropores are generated, which causes leakage of an electrolyte. Therefore, light weight and flexibility cannot be realized.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide an internal series solid-state battery which can use an aluminum foil as a bipolar current collector and avoid the defect of difficult processing when a composite foil is used as the bipolar current collector in the prior art.
In order to solve the above technical problems, the present invention provides an internal series solid-state battery comprising two or more battery cells, each of which comprises a current collector, a solid-state electrolyte layer, and an electrode layer formed of a positive electrode layer and a negative electrode layer; the two or more battery units form a series-connection type solid-state battery in a superposition mode, and two adjacent battery units are superposed to enable a current collector of one battery unit to contact an electrode layer of the other battery unit;
the current collector is an aluminum current collector, and the negative electrode layer is a niobium oxide layer.
Further, the battery units comprise a current collector, an anode layer, a solid electrolyte layer and a cathode layer which are sequentially stacked, and the adjacent two battery units are stacked to enable the current collector of one battery unit to contact with the cathode layer of the next battery unit so as to obtain the internal series connection type solid battery.
Further, the internal series solid-state battery includes a first battery cell and a second battery cell, the first battery cell includes a first current collector, a first positive electrode layer, a first solid electrolyte layer, and a first negative electrode layer that are sequentially stacked, and the second battery cell includes a second current collector, a second positive electrode layer, a second solid electrolyte layer, a second negative electrode layer, and a third current collector that are sequentially stacked; the first battery cell and the second battery cell are stacked such that the second current collector is in contact with the first negative electrode layer to obtain an internal series-type solid-state battery.
Further, the material of the positive electrode layer is ternary lithium, lithium iron phosphate, lithium manganate, lithium iron manganese phosphate or lithium nickel cobalt manganate.
Further, the material of the solid electrolyte layer is lithium aluminum titanium phosphate, lithium lanthanum titanate or lithium lanthanum zirconium oxide.
Further, the thickness of the solid electrolyte layer is 50-70 μm.
The utility model also provides a solid-state battery pack, which comprises a battery pack shell and one or more internal series-type solid-state batteries, wherein the one or more internal series-type solid-state batteries are arranged in the battery pack shell and are connected in series or in parallel.
Compared with the prior art, the technical scheme of the utility model has the following advantages:
1. according to the internal series solid-state battery, the niobium oxide is used as the negative electrode material, so that the aluminum foil can be used as the bipolar current collector, and the defect that the processing is difficult when a composite foil is used as the bipolar current collector in the prior art is overcome.
2. The internal series solid-state battery solves the problem that the current collector needs to meet the requirements of oxidation resistance and reduction resistance at the same time. Compared with a lithium titanate negative electrode material, the lithium intercalation capacity and the compaction density are improved, and the energy density of the battery is further improved.
Drawings
Fig. 1 is a schematic structural view of an internal series type solid-state battery according to an embodiment of the present invention;
wherein: 1. a first current collector; 2. a first positive electrode layer; 3. a first solid electrolyte layer; 4. a first negative electrode layer; 5. a second current collector; 6. a second positive electrode layer; 7. a second solid electrolyte layer; 8. a second negative electrode layer; 9. a third current collector.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the utility model herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the utility model. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Unless otherwise specified, the reagents according to the examples of the present invention are all commercially available products, and all of them are commercially available.
As described in the background, in the internal series solid-state battery, a bipolar current collector is required, and the current collector must satisfy the characteristics of oxidation resistance and reduction resistance. And it must also ensure that the battery cell is electronically conductive while the current collector is internally insulated, and the electrolyte does not penetrate in the middle or short-circuit from the inside. At present, the commonly used aluminum foil current collector and copper foil current collector can not meet the requirement of a bipolar current collector, and enterprises generally compound metal foils together directly to form a compound foil or bond the metal foils to two sides of a viscous polymer layer. However, metal foils are generally formed by rolling, and the thickness cannot be made ultrathin; if the foil is ultrathin, holes are easily formed in the surface of the foil, and electrolyte leaks.
In order to solve the technical problem that the composite foil current collector is difficult to process, the inventor develops a new method, and still uses the commonly used aluminum foil current collector as a bipolar current collector and selects niobium oxide as a negative electrode material, thereby completing the utility model. The technical solution of the present invention is specifically explained below.
The utility model provides an internal series solid-state battery, which comprises two or more battery units, wherein each battery unit comprises a current collector, a solid-state electrolyte layer and an electrode layer formed by an anode layer and a cathode layer; the two or more battery units form a series-connection type solid-state battery in a superposition mode, and two adjacent battery units are superposed to enable a current collector of one battery unit to contact an electrode layer of the other battery unit; the current collector is an aluminum current collector, and the negative electrode layer is a niobium oxide layer. In the solid-state battery, two adjacent battery units use the same aluminum foil as current collectors of a positive electrode and a negative electrode, so that the two adjacent battery units are connected in series.
Niobium oxide is used as a negative electrode material, the potential is high, the lithium-embedded potential platform is 1.8V and higher than graphite and metal lithium, so that Al-LI alloy cannot be formed when aluminum foil is used as a current collector, and the internal series connection of the solid-state battery can be realized only by meeting the requirement of oxidation resistance. In addition, the compacted density of the niobium oxide can reach 2.7g/cc, which is much higher than that of graphite by 1.4-1.7g/cc, and the energy density of the battery is favorably improved.
At present, the technical scheme of using lithium titanate as a negative electrode material appears in the prior art, and aluminum foil can be used as a bipolar current collector. But compared with lithium titanate, niobium oxide has higher gram capacity and compaction density, and the gram capacity can reach 200mAh/g and is higher than 170mAh/g of lithium titanate; the compaction density can reach 2.7g/cc and is also higher than 1.8-1.9g/cc of lithium titanate. Therefore, the niobium oxide is used as the negative electrode material, so that the lithium intercalation capacity and the compaction density are improved, and the energy density of the battery is further improved.
In one exemplary embodiment of the present invention, the battery cell includes a current collector, a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, which are sequentially stacked in this order, and two adjacent battery cells are stacked such that the current collector of one battery cell contacts the negative electrode layer of the next battery cell to obtain an internal series type solid-state battery.
Referring to fig. 1, in another exemplary embodiment of the present invention, the internal series solid-state battery includes a first battery cell including a first current collector 1, a first positive electrode layer 2, a first solid electrolyte layer 3, and a first negative electrode layer 4, which are sequentially stacked in this order, and a second battery cell including a second current collector 5, a second positive electrode layer 6, a second solid electrolyte layer 7, a second negative electrode layer 8, and a third current collector 9, which are sequentially stacked in this order; the first battery cell and the second battery cell are stacked such that the second current collector is in contact with the first negative electrode layer to obtain an internal series-type solid-state battery.
In the utility model, the anode layer material can be selected from common anode materials known in the field, including but not limited to ternary lithium, lithium iron phosphate, lithium manganate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide and the like. It is understood that, in the preparation of the positive electrode layer, an appropriate amount of a necessary functional material such as a conductive agent, a binder, a solid electrolyte, and the like is added in addition to the above-described lithium source material. For example, in one embodiment, the formulation of the positive electrode layer material is ternary PVDF (solef 5130, HSV900, etc.) SP solid electrolyte 80:5:5: 10. Of course, the formulation of the positive electrode layer material is not limited thereto, and other suitable formulations may be used.
Similarly, in the present invention, the negative electrode material is added with an appropriate amount of necessary functional materials such as a conductive agent, a binder, and a solid electrolyte, in addition to niobium oxide. For example, in one embodiment, the formulation of the material for the negative electrode layer is niobium oxide PVDF (KF9300) SP solid electrolyte 80:5:5: 10. Of course, the formulation of the material of the negative electrode layer is not limited thereto, and other suitable formulations may be used.
In the present invention, the material of the solid electrolyte layer can be selected from commonly used solid electrolyte materials known in the art, including but not limited to lithium aluminum titanium phosphate, lithium lanthanum titanate, or lithium lanthanum zirconium oxide. The thickness of the solid electrolyte layer is 10-70 μm, preferably 50-70 μm.
In the preparation process of the series solid-state battery, after the solid-state electrolyte is prepared into slurry, the solid-state electrolyte can be coated on the surfaces of the positive electrode and the negative electrode by using the existing slurry coating mode (scraper coating, extrusion coating and transfer coating), then the positive electrode and the negative electrode are assembled by a lamination mode to obtain a battery unit, and two or more battery units are stacked to form the internal series solid-state battery.
The series-type solid-state battery of the present invention can be further assembled to form a solid-state battery pack. In one embodiment, the solid-state battery pack includes a battery pack case and one or more internal series-type solid-state batteries, wherein the one or more internal series-type solid-state batteries are housed in the battery pack case and are configured to be connected in series or in parallel.
In conclusion, the utility model realizes the internal series connection of the solid-state batteries, and solves the technical problem that the current collector needs to meet the requirements of oxidation resistance and reduction resistance at the same time under the condition of not changing the aluminum foil current collector. In addition, compared with the technical scheme of taking lithium titanate as the negative electrode material, the technical scheme of the utility model improves the lithium insertion capacity and the compaction density, and further improves the energy density of the battery.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the utility model.
Claims (7)
1. An internal series type solid-state battery comprising two or more battery cells, each of which comprises a current collector, a solid electrolyte layer, and an electrode layer formed of a positive electrode layer and a negative electrode layer; the two or more battery units form a series-connection type solid-state battery in a superposition mode, and two adjacent battery units are superposed to enable a current collector of one battery unit to contact an electrode layer of the other battery unit;
the current collector is an aluminum current collector, and the negative electrode layer is a niobium oxide layer.
2. The internal series solid-state battery according to claim 1, wherein the battery cells comprise a current collector, a positive electrode layer, a solid electrolyte layer and a negative electrode layer, which are sequentially stacked, and two adjacent battery cells are stacked such that the current collector of one battery cell contacts the negative electrode layer of the next battery cell to obtain the internal series solid-state battery.
3. The internal series-type solid state battery according to claim 1, comprising a first battery cell including a first current collector, a first positive electrode layer, a first solid electrolyte layer, a first negative electrode layer, and a second battery cell including a second current collector, a second positive electrode layer, a second solid electrolyte layer, a second negative electrode layer, and a third current collector, which are sequentially stacked; the first battery cell and the second battery cell are superposed such that the second current collector is in contact with the first negative electrode layer to obtain an internal series-type solid-state battery.
4. The internal series solid-state battery according to claim 1, wherein a material of the positive electrode layer is ternary lithium, lithium iron phosphate, lithium manganese oxide, lithium iron manganese phosphate, or lithium nickel cobalt oxide.
5. The internal series type solid-state battery according to claim 1, wherein a material of the solid electrolyte layer is lithium aluminum titanium phosphate, lithium lanthanum titanate, or lithium lanthanum zirconium oxide.
6. The internal series type solid-state battery according to claim 1, wherein the thickness of the solid electrolyte layer is 50 to 70 μm.
7. A solid-state battery comprising a battery housing and one or more internal series solid-state batteries according to any one of claims 1 to 6, wherein the one or more internal series solid-state batteries are housed in the battery housing and are configured to be connected in series or in parallel.
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| CN202220117266.4U CN217035901U (en) | 2022-01-17 | 2022-01-17 | Internal series solid-state battery and solid-state battery pack |
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| CN202220117266.4U CN217035901U (en) | 2022-01-17 | 2022-01-17 | Internal series solid-state battery and solid-state battery pack |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024077591A1 (en) * | 2022-10-14 | 2024-04-18 | 宁德时代新能源科技股份有限公司 | Internally serial battery and electric apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024077591A1 (en) * | 2022-10-14 | 2024-04-18 | 宁德时代新能源科技股份有限公司 | Internally serial battery and electric apparatus |
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