WO2022116964A1 - 一种电极组件及包含其的电化学装置、电子装置 - Google Patents
一种电极组件及包含其的电化学装置、电子装置 Download PDFInfo
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- WO2022116964A1 WO2022116964A1 PCT/CN2021/134394 CN2021134394W WO2022116964A1 WO 2022116964 A1 WO2022116964 A1 WO 2022116964A1 CN 2021134394 W CN2021134394 W CN 2021134394W WO 2022116964 A1 WO2022116964 A1 WO 2022116964A1
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- Prior art keywords
- layer
- electrode assembly
- negative electrode
- lithium
- active layer
- Prior art date
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- CLDYDTBRUJPBGU-UHFFFAOYSA-N butyl 2,2,2-trifluoroacetate Chemical compound CCCCOC(=O)C(F)(F)F CLDYDTBRUJPBGU-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BPTOPBBYWGYDGS-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-yne Chemical compound OC(O)=O.FC(F)(F)C#C BPTOPBBYWGYDGS-UHFFFAOYSA-N 0.000 description 1
- XWHYSFLTVBWGDX-UHFFFAOYSA-N carbonic acid;3-ethylpenta-1,2-diene Chemical compound OC(O)=O.CCC(CC)=C=C XWHYSFLTVBWGDX-UHFFFAOYSA-N 0.000 description 1
- DOAYJNMCHKRFLA-UHFFFAOYSA-N carbonic acid;hex-3-yne Chemical compound OC(O)=O.CCC#CCC DOAYJNMCHKRFLA-UHFFFAOYSA-N 0.000 description 1
- SYLNJGIBLUVXCG-UHFFFAOYSA-N carbonic acid;prop-1-yne Chemical compound CC#C.OC(O)=O SYLNJGIBLUVXCG-UHFFFAOYSA-N 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
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- 239000001913 cellulose Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- GIPIUENNGCQCIT-UHFFFAOYSA-K cobalt(3+) phosphate Chemical class [Co+3].[O-]P([O-])([O-])=O GIPIUENNGCQCIT-UHFFFAOYSA-K 0.000 description 1
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- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
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- LMEDOLJKVASKTP-UHFFFAOYSA-N dibutyl sulfate Chemical compound CCCCOS(=O)(=O)OCCCC LMEDOLJKVASKTP-UHFFFAOYSA-N 0.000 description 1
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- NIQAXIMIQJNOKY-UHFFFAOYSA-N ethyl 2,2,2-trifluoroethyl carbonate Chemical compound CCOC(=O)OCC(F)(F)F NIQAXIMIQJNOKY-UHFFFAOYSA-N 0.000 description 1
- HHEIMYAXCOIQCJ-UHFFFAOYSA-N ethyl 2,2-dimethylpropanoate Chemical compound CCOC(=O)C(C)(C)C HHEIMYAXCOIQCJ-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
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- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
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- 101150004907 litaf gene Proteins 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
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- VQGVEHXXEPMALY-UHFFFAOYSA-N lithium;dihydrogen borate;propanedioic acid Chemical class [Li+].OB(O)[O-].OC(=O)CC(O)=O VQGVEHXXEPMALY-UHFFFAOYSA-N 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical group [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CHCLGECDSSWNCP-UHFFFAOYSA-N methoxymethoxyethane Chemical compound CCOCOC CHCLGECDSSWNCP-UHFFFAOYSA-N 0.000 description 1
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 1
- YLJRCXSSKLWCDE-UHFFFAOYSA-N methyl ethanesulfonate Chemical compound CCS(=O)(=O)OC YLJRCXSSKLWCDE-UHFFFAOYSA-N 0.000 description 1
- MBXNQZHITVCSLJ-UHFFFAOYSA-N methyl fluorosulfonate Chemical compound COS(F)(=O)=O MBXNQZHITVCSLJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- YSYBYIDPNZPQLJ-UHFFFAOYSA-N methyl trifluoromethyl carbonate Chemical compound COC(=O)OC(F)(F)F YSYBYIDPNZPQLJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
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- WCWOFOOEGIRFKM-UHFFFAOYSA-N pentane-1,3-diol sulfurous acid Chemical compound S(=O)(O)O.C(CC(CC)O)O WCWOFOOEGIRFKM-UHFFFAOYSA-N 0.000 description 1
- IWYYMJCDQBNSPY-UHFFFAOYSA-N pentane-1,4-diol sulfuric acid Chemical compound S(=O)(=O)(O)O.C(CCC(C)O)O IWYYMJCDQBNSPY-UHFFFAOYSA-N 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
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- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- ZDOOXJCSVYVMQL-UHFFFAOYSA-N tris(2,2,3,3,3-pentafluoropropyl) phosphate Chemical compound FC(F)(F)C(F)(F)COP(=O)(OCC(F)(F)C(F)(F)F)OCC(F)(F)C(F)(F)F ZDOOXJCSVYVMQL-UHFFFAOYSA-N 0.000 description 1
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- 238000004804 winding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present application relates to the field of energy storage, and in particular, to an electrode assembly for improving the safety of a cell and increasing energy density, and an electrochemical device and an electronic device including the electrode assembly.
- lithium-ion batteries With the development of technology and the increase in demand for mobile devices, the demand for electrochemical devices (eg, lithium-ion batteries) has increased significantly. At the same time, lithium-ion batteries with high safety and high energy density are one of the research directions.
- the electrochemical device In actual use, the electrochemical device will be hit by a foreign object, and in extreme cases, it will be pierced by a sharp object.
- the electrochemical device When the electrochemical device is pierced, on the one hand, if the piercing object is a metal body, the The piercing part of the fluid is connected to the other electrode through the metal body; on the other hand, the piercing part of the current collector usually produces burrs, which deform and extend downward with the piercing object, thereby piercing the diaphragm to connect the positive electrode and the electrode.
- the negative electrode is directly connected, resulting in the occurrence of a short circuit, which in turn generates a large amount of heat, causing the battery to catch fire or even explode, which seriously threatens the safety of consumers.
- consumers have higher requirements for the capacity and battery life of electrochemical devices.
- the embodiments of the present application solve at least one problem in the related art to at least some extent by providing an electrode assembly that improves cell safety and increases energy density and an electrochemical device including the same.
- the present application provides an electrode assembly comprising a negative electrode current collector, a negative electrode active layer disposed on at least one surface of the negative electrode current collector, a diaphragm layer, and a positive electrode active layer, the diaphragm layer being disposed on There is no positive metal current collector between the negative electrode active layer and the positive electrode active layer, and at least part of the surface of the positive electrode active layer along the projection area perpendicular to the part of the surface.
- the partial surface accounts for more than 50% of the surface of the positive electrode active layer, preferably more than 80%, more preferably more than 95%.
- the positive electrode only includes a positive electrode active layer, and no metal current collector is required. This arrangement can reduce the overall thickness of the electrode assembly and improve the energy density of the electrode.
- the metal current collectors described in this application include current collectors made of metal materials such as aluminum foil, copper foil, and stainless steel foil.
- the adhesion between the positive electrode active layer and the separator layer is greater than or equal to 2 N/m.
- the positive electrode active layer includes a positive electrode active material, wherein the positive electrode active material is selected from at least one of a lithium transition metal composite oxide and a lithium-containing transition metal phosphate compound.
- the negative electrode active layer includes a negative electrode active material and an adhesive, wherein the negative electrode active material is selected from at least one of graphite and silicon-based materials.
- the silicon-based material is selected from at least one of pure silicon, SiOx (0 ⁇ x ⁇ 2), and silicon-carbon composite.
- the negative electrode active layer may be coated on one surface of the negative electrode current collector, or may be coated on two opposite surfaces of the negative electrode current collector.
- the separator layer, the positive active material layer and the conductive layer can be coated on both sides of the negative electrode current collector to form an electrode assembly that is symmetrical with respect to the negative electrode current collector.
- the surface of the positive electrode active layer is provided with a conductive layer.
- the thickness of the conductive layer is 0.1 ⁇ m to 30 ⁇ m.
- the thickness of the electrode assembly is closely related to the energy density, and the conductive layer should not be too thin or too thick. If the thickness of the conductive layer is too small, in addition to increasing the difficulty of the process, the thickness of the conductive layer will also be uneven, resulting in poor conductivity. If the thickness of the conductive layer is too large, the thickness of the entire electrode assembly will be too large, which will eventually reduce the energy density of the electrode assembly. In the present application, the thickness of the conductive layer is 0.1 m to 30 m.
- the conductive layer in the electrode assembly includes a conductive agent, wherein the conductive agent includes at least one of carbon black, acetylene black, fullerene, carbon nanotube, graphene, and graphite.
- the surface of the conductive layer is provided with an insulating layer.
- the insulating layer includes a binder, wherein based on the weight of the insulating layer, the mass percentage of the binder is a, wherein 2% ⁇ a ⁇ 100%. Adding a binder to the insulating layer can enhance the adhesion between the insulating materials, so that the insulating layer can be firmly adhered to the surface of the conductive layer.
- the binder can be selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), nitrile rubber, polyurethane, At least one of fluorinated rubber, polyvinyl alcohol (PVA) or sodium polyacrylate.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- CMC carboxymethyl cellulose
- SBR styrene butadiene rubber
- nitrile rubber polyurethane
- At least one of fluorinated rubber At least one of fluorinated rubber, polyvinyl alcohol (PVA) or sodium polyacrylate.
- the insulating layer composition further includes an insulating material, and the insulating layer has a thickness h ⁇ 0.5 ⁇ m.
- the insulating material in the insulating layer may be an inorganic insulating material, or at least one of organic insulating materials, or a mixed material of an inorganic insulating material and an organic insulating material.
- the inorganic insulating material may be selected from at least one of BaSO 4 , CaSiO 3 , ⁇ -AlOOH, CaSiO 4 , Al 2 O 3 , TiO 2
- the organic insulating material may be selected from ethylene, vinyl chloride, propylene, At least one of homopolymers or copolymers of styrene, butadiene, vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
- the insulating material has an average particle size of 0.01 ⁇ m to 20 ⁇ m.
- the separator layer includes at least one of an inorganic layer and a polyolefin porous layer.
- the composition of the inorganic layer includes inorganic particles and a binder, wherein the inorganic particles include BaSO 4 , CaSiO 3 , ⁇ -AlOOH, CaSiO 4 , Al 2 O 3 , TiO 2 , At least one of SiO2 .
- the content of the binder is b based on the weight of the inorganic layer, wherein 5% ⁇ b ⁇ 40%.
- the negative electrode current collector is selected from copper foil. Copper foil has excellent stability and can avoid corrosion during discharge.
- the electrode assembly further includes tabs.
- the tab is a positive electrode tab, and the positive electrode tab is in contact with the positive electrode active layer, thereby realizing the electrical connection between the positive electrode tab and the positive electrode active layer.
- the positive electrode tabs are in contact with the conductive layer, thereby achieving electrical connection between the tabs and the conductive layer.
- the present application also provides a method for preparing the aforementioned electrode assembly, comprising the following steps: 1) sequentially disposing the negative electrode active layer and the diaphragm layer on the surface of the negative electrode current collector; 2) coating the surface of the diaphragm layer the positive active layer.
- it further comprises the step of: 3) disposing the conductive layer or the insulating layer on the surface of the positive electrode active layer.
- it further comprises the step of: 4) disposing the insulating layer on the surface of the conductive layer.
- the present application also provides an electrochemical device comprising the electrode assembly of the present invention.
- the present application also provides an electronic device comprising the electrochemical device described in the present application.
- the positive electrode includes a positive electrode active layer and a conductive layer, no metal current collector (eg, aluminum) is required, and the thickness of the entire electrode assembly can be reduced, thereby achieving higher energy density.
- the positive electrode does not have a metal current collector, it can avoid short circuit caused by metal burrs piercing the separator when it is pierced. Therefore, the secondary battery (eg, lithium ion battery) employing the present application has higher safety.
- FIG. 1 is a schematic diagram of an embodiment of the electrode assembly of the present application
- FIG. 2 is a schematic diagram of another embodiment of the electrode assembly of the present application.
- FIG. 3 is a schematic diagram of yet another embodiment of the electrode assembly of the present application.
- a list of items joined by the terms "at least one of,” “at least one of,” “at least one of,” or other similar terms may mean the listed items any combination of .
- the phrase “at least one of A and B” means A only; B only; or A and B.
- the phrase "at least one of A, B, and C” means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
- Item A may contain a single element or multiple elements.
- Item B may contain a single element or multiple elements.
- Item C may contain a single element or multiple elements.
- Electrodes (positive or negative electrodes) of electrochemical devices are typically prepared by mixing active materials, conductive agents, thickeners, binders, and solvents, and then coating the mixed slurry on the collector.
- the electrochemical device is pierced, on the one hand, if the pierced object is a metal body, the pierced part of the current collector is connected to another electrode through the metal body; on the other hand, the pierced part of the current collector is Usually, burrs are generated and extend downward with the piercing object, so as to pierce the separator to directly connect the positive and negative electrodes, resulting in the occurrence of a short circuit.
- the present application eliminates the traditional Al foil for positive current collectors, and avoids the high ductility of the metal current collector Al foil during the process of piercing the electrochemical device.
- the contact of the electrodes also avoids the generation of metal burrs, thereby piercing the isolation membrane and causing a short circuit, thereby improving the safety of the electrochemical device.
- the elimination of inactive metal current collectors in electrochemical devices also greatly improves the energy density.
- the present application provides an electrochemical device comprising an electrode assembly of a negative electrode, a positive electrode and a separator layer as described below, and an electrolyte.
- the negative electrode includes a negative electrode current collector and a negative electrode active layer disposed on one or both surfaces of the negative electrode current collector.
- the negative electrode active layer may be one or more layers, and each of the multilayer negative electrode active layers may contain the same or different negative electrode active materials.
- the negative electrode active material is any material that can reversibly intercalate and deintercalate metal ions such as lithium ions.
- the chargeable capacity of the negative active layer is greater than the discharge capacity of the positive active layer to prevent unintentional precipitation of lithium metal on the negative electrode during charging.
- any known current collector can be used.
- negative electrode current collectors include, but are not limited to, metal materials such as aluminum, copper, nickel, stainless steel, nickel-plated steel, and the like.
- the anode current collector is copper.
- the negative electrode current collector form may include, but is not limited to, metal foil, metal cylinder, metal coil, metal plate, metal film, metal mesh, stamped metal, foamed metal, etc.
- the negative electrode current collector is a thin metal film.
- the negative electrode current collector is copper foil.
- the negative electrode current collector is a rolled copper foil based on a rolling method or an electrolytic copper foil based on an electrolytic method.
- the thickness of the negative current collector is greater than 1 ⁇ m or greater than 5 ⁇ m. In some embodiments, the thickness of the negative current collector is less than 100 ⁇ m or less than 50 ⁇ m. In some embodiments, the thickness of the negative electrode current collector is within a range composed of any two of the above-mentioned values.
- the negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium ions.
- Examples of negative electrode active materials may include, but are not limited to, carbon materials such as natural graphite and artificial graphite; silicon-based materials such as pure silicon (Si), silicon oxide, silicon-carbon composites, alloys of silicon and metal elements, and the like.
- the negative electrode active materials may be used alone or in combination.
- the negative electrode active layer may further include a negative electrode binder.
- the negative electrode binder can improve the bonding of the negative electrode active material particles to each other and the bonding of the negative electrode active material to the current collector.
- the type of the negative electrode binder is not particularly limited, as long as it is a material that is stable to the electrolyte solution or the solvent used in the production of the electrode.
- the negative electrode binder includes a resin binder. Examples of resin binders include, but are not limited to, fluororesins, polyacrylonitrile (PAN), polyimide resins, acrylic resins, polyolefin resins, and the like.
- the negative electrode binder includes, but is not limited to, carboxymethyl cellulose (CMC) or its salt, styrene-butadiene rubber (SBR), polyacrylic acid (PAA) or Its salts, polyvinyl alcohol, etc.
- CMC carboxymethyl cellulose
- SBR styrene-butadiene rubber
- PAA polyacrylic acid
- Its salts polyvinyl alcohol, etc.
- the negative electrode can be prepared by the following method: coating a negative electrode mixture slurry containing a negative electrode active material, a resin binder, etc. on the negative electrode current collector, and after drying, rolling is performed to form a negative electrode active layer on both sides of the negative electrode current collector. get negative.
- the positive electrode includes a positive electrode active layer, and a conductive layer may be further provided on the surface of the positive electrode active layer. According to some embodiments of the present application, an insulating layer may be further provided on the surface of the conductive layer.
- the positive electrode active layer contains a positive electrode active material.
- the positive electrode active layer may be one or more layers, and each layer of the multi-layered positive electrode active layers may contain the same or different positive electrode active materials.
- the positive active material is any material that can reversibly intercalate and deintercalate metal ions such as lithium ions.
- the discharge capacity of the positive active layer is less than the rechargeable capacity of the negative active layer to prevent unintentional precipitation of lithium metal on the negative electrode during charging.
- the type of the positive electrode active material is not particularly limited as long as it can electrochemically occlude and release metal ions (eg, lithium ions).
- the positive active material is a material containing lithium and at least one transition metal.
- the positive electrode active material may include, but are not limited to, lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds.
- the transition metal in the lithium transition metal composite oxide includes V, Ti, Cr, Mn, Fe, Co, Ni, Cu, and the like.
- the lithium transition metal composite oxides include lithium cobalt composite oxides such as LiCoO 2 ; lithium nickel composite oxides such as LiNiO 2 ; lithium manganese composite oxides such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 4 ; LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 and other lithium-nickel-manganese-cobalt composite oxides, in which a part of the transition metal atoms serving as the host of these lithium transition metal composite oxides are Substituted by other elements such as Na, K, B, F, Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, Nb, Mo, Sn, W, etc.
- lithium transition metal composite oxide may include, but are not limited to, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , LiNi 0.45 Co 0.10 Al 0.45 O 2 , LiMn 1.8 Al 0.2 O 4 and LiMn 1.5 Ni 0.5 O 4 and so on.
- combinations of lithium transition metal composite oxides include, but are not limited to, combinations of LiCoO 2 and LiMn 2 O 4 , wherein a portion of Mn in LiMn 2 O 4 may be replaced by transition metals (eg, LiNi 0.33 Co 0.33 Mn 0.33 O 2 ), a part of Co in LiCoO 2 can be replaced by transition metals.
- the transition metal in the lithium-containing transition metal phosphate compound includes V, Ti, Cr, Mn, Fe, Co, Ni, Cu, and the like.
- the lithium-containing transition metal phosphate compounds include LiFePO 4 , Li 3 Fe 2 (PO 4 ) 3 , LiFeP 2 O 7 and other iron phosphates, and LiCoPO 4 and other cobalt phosphates, wherein as these lithium transition metal phosphate compounds A part of the transition metal atoms of the host is replaced by Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and other elements.
- a powdered material of lithium transition metal oxide Li a M b O 2 is used, wherein 0.9 ⁇ a ⁇ 1.1, 0.9 ⁇ b ⁇ 1.1, and M is primarily a transition metal selected from Mn, Co, and Ni , where the composition M varies with particle size.
- A is selected from at least one of the elements Al, Mg, Ti, Cr, and A' At least one selected from elements F, Cl, S, Zr, Ba, Y, Ca, B, Be, Sn, Sb, Na, and Zn.
- powders with a composition that is related to size ie one component with large particles (eg distributed centered at ⁇ 20 ⁇ m); the component is capable of rapid bulk diffusion.
- Another component has small particles (eg distributed around 5 ⁇ m) and its composition ensures safety.
- an electrode active material is provided that combines high cycle stability and high safety with high volumetric and high gravimetric energy density.
- the positive electrode active material has a broad particle size distribution, which is defined as a particle size ratio of large particles to small particles greater than 3, and Dv90/Dv10>3, wherein Dv90 represents the particle size distribution on a volume basis, from small to small From the particle size side, the particle size reaches 90% of the cumulative volume.
- Dv10 represents a particle size that reaches 10% of the cumulative volume from the small particle size side in the particle size distribution based on volume.
- the particle size distribution of the powder can be determined by suitable methods known in the art. Suitable methods are eg laser diffraction or sieving by using sets of sieves with different mesh numbers.
- the individual particles are substantially lithium transition metal oxides, and the individual particles have Co, whose content in the transition metal increases continuously with particle size.
- the individual particles also contain Mn in the transition metal, and the Mn content decreases continuously with particle size.
- the large particles have large particles close to the composition of LiCoO2 to achieve high Li diffusion constants, and thus to achieve adequate rate performance.
- Large particles occupy only a small fraction of the total surface area of the positive electrode. Therefore, the heat released by the reaction with the electrolyte at the surface or at the outer part is limited; as a result, there are fewer large particles leading to poor safety.
- Small particles have compositions containing less Co for increased safety. The lower lithium diffusion constant is acceptable in small particles without significant loss of rate performance due to the short length of the solid-state diffusion paths.
- the preferred composition of the small particles contains smaller amounts of Co and larger amounts of stabilizing elements, such as Mn.
- the slower Li bulk diffusion is acceptable, but the stability of the surface is high.
- the preferred composition of large particles contains a larger amount of Co and a smaller amount of Mn, due to the need for rapid lithium diffusion, while a slightly lower surface stability is acceptable.
- preferably at least 80 w% of the M is cobalt or nickel in the interior of a single particle composed of LixMO2 .
- the inner portion of the particle has a composition close to LiCoO 2 .
- the outer part is lithium manganese nickel cobalt oxide.
- the preparation of the electrode active material having a composition and size-dependent powdery form can be accomplished by depositing at least one transition metal-containing precipitate on seed particles, the seed particles having a transition metal composition different from that of the precipitate; A controlled amount of a lithium source is added; and at least one thermal treatment is performed wherein substantially all of the particles obtained contain a seed-derived inner core completely covered by a precipitate-derived layer.
- the conductive layer conducts current of the positive electrode and at least partially covers at least one surface of the positive electrode.
- the thickness of the conductive layer is 0.1 ⁇ m to 30 ⁇ m.
- the conductive layer includes a conductive agent, and the conductive agent includes at least one of carbon black, acetylene black, fullerene, carbon nanotube, graphene, and graphite.
- an insulating layer is provided on the surface of the conductive layer.
- the insulating layer includes an adhesive.
- the insulating layer further includes an insulating material.
- the mass percentage content of the binder is a, wherein 2% ⁇ a ⁇ 100%, and the mass percentage content of the insulating material is 1-a.
- the insulating material includes at least one of an inorganic insulating material and/or an organic insulating material.
- the inorganic insulating material includes at least one of BaSO 4 , CaSiO 3 , ⁇ -AlOOH, CaSiO 4 , Al 2 O 3 , and TiO 2 ;
- the organic insulating material includes ethylene, vinyl chloride , at least one of homopolymers or copolymers of propylene, styrene, butadiene, vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
- the particle size D50 of the insulating material is 0.01 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m to 5 ⁇ m.
- the particle size of the insulating material is within this range, the dispersion uniformity of the insulating material in the layer and the thickness of the insulating layer coating can be ensured.
- the thickness h of the insulating layer is greater than or equal to 0.5 ⁇ m.
- the binder includes polyvinylidene fluoride PVDF, polytetrafluoroethylene PTFE, sodium carboxymethyl cellulose CMC, styrene butadiene rubber SBR, nitrile rubber, polyurethane, fluorine rubber, polystyrene At least one of vinyl alcohol PVA and sodium polyacrylate.
- a separator layer is provided between the positive electrode and the negative electrode.
- the separator layer may be provided between the positive electrode and the negative electrode in a conventionally known manner.
- the surface of the electrode is formed by coating the slurry, or by electrospinning on the surface of the electrode, or by stacking the pre-prepared separator with the positive and negative electrodes in a conventional stacking manner.
- the separator layer when the surface of the electrode is coated with slurry, the separator layer includes inorganic particles and a binder, and the binder is selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), carboxymethyl At least one of sodium cellulose (CMC), styrene-butadiene rubber (SBR), nitrile rubber, polyurethane, fluorinated rubber, polyvinyl alcohol (PVA), and sodium polyacrylate.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- CMC sodium cellulose
- SBR styrene-butadiene rubber
- PVA polyvinyl alcohol
- the inorganic particles include at least one of BaSO 4 , CaSiO 3 , ⁇ -AlOOH, CaSiO 4 , Al 2 O 3 , TiO 2 , SiO 2 .
- the particle size D50 of the inorganic particles is 0.01 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m to 5 ⁇ m.
- the thickness of the diaphragm layer is arbitrary. In some embodiments, the thickness of the membrane layer is greater than 1 ⁇ m, greater than 5 ⁇ m, or greater than 8 ⁇ m. In some embodiments, the thickness of the membrane layer is less than 50 ⁇ m, less than 40 ⁇ m, or less than 30 ⁇ m. In some embodiments, the thickness of the diaphragm layer is in the range composed of any two of the above-mentioned values. When the thickness of the separator layer is within the above range, insulating properties and mechanical strength can be ensured, and rate characteristics and energy density of the electrochemical device can be ensured.
- the porosity of the separator layer is arbitrary. In some embodiments, the porosity of the membrane layer is greater than 20%, greater than 35%, or greater than 45%. In some embodiments, the membrane layer has a porosity of less than 90%, less than 85%, or less than 75%. In some embodiments, the porosity of the separator layer is within a range consisting of any two of the above-mentioned values. When the porosity of the separator layer is within the above range, insulating properties and mechanical strength can be ensured, and membrane resistance can be suppressed, so that the electrochemical device has good rate characteristics.
- the average pore diameter of the separator layer is also arbitrary.
- the membrane layer has an average pore size of less than 0.5 ⁇ m or less than 0.2 ⁇ m. In some embodiments, the membrane layer has an average pore size greater than 0.05 ⁇ m. In some embodiments, the average pore size of the membrane layer is within a range composed of any two of the above-mentioned values. When the average pore diameter of the separator layer exceeds the above-mentioned range, a short circuit is likely to occur. When the average pore diameter of the separator layer is within the above range, the membrane resistance can be suppressed while preventing short circuit, so that the electrochemical device has good rate characteristics.
- the electrolytic solution used in the electrochemical device of the present application includes an electrolyte and a solvent that dissolves the electrolyte.
- the electrolyte used in the electrochemical devices of the present application further includes additives.
- the electrolyte further comprises any non-aqueous solvent known in the art as a solvent for the electrolyte.
- the non-aqueous solvent includes, but is not limited to, one or more of the following: cyclic carbonate, chain carbonate, cyclic carboxylate, chain carboxylate, cyclic carbonate Ethers, chain ethers, phosphorus-containing organic solvents, sulfur-containing organic solvents and aromatic fluorine-containing solvents.
- examples of the cyclic carbonate may include, but are not limited to, one or more of the following: ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate.
- the cyclic carbonate has 3-6 carbon atoms.
- examples of the chain carbonate may include, but are not limited to, one or more of the following: dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate (DEC), methyl carbonate n-propyl carbonate, ethyl-n-propyl carbonate, di-n-propyl carbonate and other chain carbonates, etc.
- fluorine-substituted chain carbonates may include, but are not limited to, one or more of the following: bis(fluoromethyl)carbonate, bis(difluoromethyl)carbonate, bis(trifluoromethyl)carbonate base) carbonate, bis(2-fluoroethyl)carbonate, bis(2,2-difluoroethyl)carbonate, bis(2,2,2-trifluoroethyl)carbonate, 2-fluoroethyl methyl carbonate, 2,2-difluoroethyl methyl carbonate and 2,2,2-trifluoroethyl methyl carbonate, etc.
- examples of the cyclic carboxylate may include, but are not limited to, one or more of the following: one or more of gamma-butyrolactone and gamma-valerolactone.
- some of the hydrogen atoms of the cyclic carboxylate may be replaced by fluorine.
- examples of the chain carboxylates may include, but are not limited to, one or more of the following: methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate Ester, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl butyrate, ethyl butyrate, butyric acid Propyl, methyl isobutyrate, ethyl isobutyrate, methyl valerate, ethyl valerate, methyl pivalate and ethyl pivalate, etc.
- some of the hydrogen atoms of the chain carboxylate may be replaced by fluorine.
- examples of fluorine-substituted chain carboxylates may include, but are not limited to, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, butyl trifluoroacetate, and trifluoroacetic acid 2,2,2-trifluoroethyl ester, etc.
- examples of the cyclic ether may include, but are not limited to, one or more of the following: tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 2-methyl 1,3-dioxolane, 4-methyl 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane and dimethoxypropane.
- examples of the chain ethers may include, but are not limited to, one or more of the following: dimethoxymethane, 1,1-dimethoxyethane, 1,2- Dimethoxyethane, diethoxymethane, 1,1-diethoxyethane, 1,2-diethoxyethane, ethoxymethoxymethane, 1,1-ethoxy Methoxyethane and 1,2-ethoxymethoxyethane, etc.
- examples of the phosphorus-containing organic solvent may include, but are not limited to, one or more of the following: trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl phosphate Diethyl, Ethylene Methyl Phosphate, Ethylene Ethyl Phosphate, Triphenyl Phosphate, Trimethyl Phosphite, Triethyl Phosphite, Triphenyl Phosphite, Tris(2,2,2-Phosphate) trifluoroethyl) ester and tris(2,2,3,3,3-pentafluoropropyl) phosphate and the like.
- examples of the sulfur-containing organic solvent may include, but are not limited to, one or more of the following: sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethylsulfone, dimethysulfone Ethyl sulfone, ethyl methyl sulfone, methyl propyl sulfone, dimethyl sulfoxide, methyl methanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, dimethyl sulfate , diethyl sulfate and dibutyl sulfate.
- some of the hydrogen atoms of the sulfur-containing organic solvent may be replaced by fluorine.
- the aromatic fluorine-containing solvent includes, but is not limited to, one or more of the following: fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene and trifluoromethylbenzene.
- the solvent used in the electrolyte of the present application includes cyclic carbonate, chain carbonate, cyclic carboxylate, chain carboxylate, and combinations thereof.
- the solvent used in the electrolyte of the present application includes ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl propionate, propyl propionate, n-propyl acetate, or ethyl acetate at least one of them.
- the solvent used in the electrolyte of the present application comprises: ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl propionate, propyl propionate, ⁇ -butyrolactone and combinations thereof .
- the chain carboxylate and/or cyclic carboxylate can form a passivation film on the surface of the electrode, thereby improving the intermittent charging of the electrochemical device Capacity retention after cycling.
- the electrolyte contains 1% to 60% of chain carboxylates, cyclic carboxylates, and combinations thereof.
- the electrolyte contains ethyl propionate, propyl propionate, ⁇ -butyrolactone and a combination thereof, based on the total weight of the electrolyte, the content of the combination is 1% to 60%, 10% % to 60%, 10% to 50%, 20% to 50%.
- the electrolyte contains 1% to 60%, 10% to 60%, 20% to 50%, 20% to 40%, or 30% propyl propionate based on the total weight of the electrolyte .
- examples of the additives may include, but are not limited to, one or more of the following: fluorocarbonates, ethylene carbonate containing carbon-carbon double bonds, compounds containing sulfur-oxygen double bonds, and acid anhydrides .
- the additive is present in an amount of 0.01% to 15%, 0.1% to 10%, or 1% to 5% based on the total weight of the electrolyte.
- the content of the propionate is 1.5 to 30 times, 1.5 to 20 times, 2 to 20 times, or 5-20 times that of the additive.
- the additive comprises one or more fluorocarbonates.
- fluorocarbonate can act together with propionate to form a stable protective film on the surface of the negative electrode, thereby inhibiting the decomposition reaction of the electrolyte.
- examples of the fluorocarbonate may include, but are not limited to, one or more of the following: fluoroethylene carbonate, cis-4,4-difluoroethylene carbonate, trans-4 ,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4-fluoro-4-methyl ethylene carbonate, 4-fluoro-5-methyl ethylene carbonate, trifluoromethyl methyl carbonate , trifluoroethyl methyl carbonate and ethyl trifluoroethyl carbonate, etc.
- the additive comprises one or more ethylene carbonates containing carbon-carbon double bonds.
- the carbon-carbon double bond-containing vinyl carbonate may include, but are not limited to, one or more of the following: vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, carbonic acid-1 ,2-Dimethyl vinylene carbonate, 1,2-diethyl vinylene carbonate, fluorovinylene carbonate, trifluoromethyl vinylene carbonate; vinyl ethylene carbonate, 1-methyl carbonate Ethyl-2-vinylethylene carbonate, 1-ethyl-2-vinylethylene carbonate, 1-n-propyl-2-vinylethylene carbonate, 1-methyl-2-ethylene carbonate Ethylene carbonate, 1,1-divinylethylene carbonate, 1,2-divinylethylene carbonate, 1,1-dimethyl-2-methylene carbonate and 1,1-diethyl-2-methylene ethylene carbonate, etc.
- the carbon-carbon double bond may include, but are not limited to
- the additive comprises one or more sulfur-oxygen double bond-containing compounds.
- the sulfur-oxygen double bond-containing compound may include, but are not limited to, one or more of the following: cyclic sulfate, chain sulfate, chain sulfonate, cyclic sulfonate, chain Sulfites and cyclic sulfites, etc.
- Examples of the cyclic sulfate may include, but are not limited to, one or more of the following: 1,2-ethylene glycol sulfate, 1,2-propylene glycol sulfate, 1,3-propylene glycol sulfate, 1 ,2-Butanediol sulfate, 1,3-butanediol sulfate, 1,4-butanediol sulfate, 1,2-pentanediol sulfate, 1,3-pentanediol sulfate, 1 , 4-pentanediol sulfate and 1,5-pentanediol sulfate, etc.
- chain sulfate may include, but are not limited to, one or more of the following: dimethyl sulfate, methyl ethyl sulfate, diethyl sulfate, and the like.
- chain sulfonate may include, but are not limited to, one or more of the following: fluorosulfonates such as methyl fluorosulfonate and ethyl fluorosulfonate, methyl methanesulfonate, methanesulfonic acid Ethyl ester, butyl dimethanesulfonate, methyl 2-(methanesulfonyloxy) propionate, and ethyl 2-(methanesulfonyloxy) propionate, etc.
- fluorosulfonates such as methyl fluorosulfonate and ethyl fluorosulfonate, methyl methanesulfonate, methanesulfonic acid Ethyl ester, butyl dimethanesulfonate, methyl 2-(methanesulfonyloxy) propionate, and ethyl 2-(methanesulfonyloxy) propionate, etc
- Examples of the cyclic sulfonate may include, but are not limited to, one or more of the following: 1,3-propanesultone, 1-fluoro-1,3-propanesultone, 2- Fluoro-1,3-propanesultone, 3-fluoro-1,3-propanesultone, 1-methyl-1,3-propanesultone, 2-methyl-1,3- propane sultone, 3-methyl-1,3-propane sultone, 1-propene-1,3-sultone, 2-propene-1,3-sultone, 1-fluoro -1-Propene-1,3-sultone, 2-fluoro-1-propene-1,3-sultone, 3-fluoro-1-propene-1,3-sultone, 1- Fluoro-2-propene-1,3-sultone, 2-fluoro-2-propene-1,3-sultone, 3-fluoro-2-propene-1,3-sultone, 1 -Methyl-1-prop
- chain sulfites may include, but are not limited to, one or more of the following: dimethyl sulfite, methyl ethyl sulfite, diethyl sulfite, and the like.
- cyclic sulfites may include, but are not limited to, one or more of the following: 1,2-ethylene glycol sulfite, 1,2-propylene glycol sulfite, 1,3-propylene glycol sulfite , 1,2-butanediol sulfite, 1,3-butanediol sulfite, 1,4-butanediol sulfite, 1,2-pentanediol sulfite, 1,3-pentanediol sulfite Glycol sulfite, 1,4-pentanediol sulfite and 1,5-pentanediol sulfite, etc.
- the additive comprises one or more acid anhydrides.
- the acid anhydride may include, but are not limited to, one or more of cyclic phosphoric anhydride, carboxylic acid anhydride, disulfonic acid anhydride, and carboxylic acid sulfonic acid anhydride.
- the cyclic phosphoric anhydride may include, but are not limited to, one or more of trimethylphosphoric acid cyclic anhydride, triethylphosphoric acid cyclic anhydride, and tripropylphosphoric acid cyclic anhydride.
- the carboxylic anhydride may include, but are not limited to, one or more of succinic anhydride, glutaric anhydride, and maleic anhydride.
- Examples of the disulfonic anhydride may include, but are not limited to, one or more of ethane disulfonic anhydride and propane disulfonic anhydride.
- Examples of the carboxylic acid sulfonic anhydride may include, but are not limited to, one or more of sulfobenzoic anhydride, sulfopropionic anhydride, and sulfobutyric anhydride.
- the additive is a combination of a fluorocarbonate and a carbon-carbon double bond-containing ethylene carbonate. In some embodiments, the additive is a combination of a fluorocarbonate and a compound containing a sulfur-oxygen double bond. In some embodiments, the additive is a combination of a fluorocarbonate and a compound having 2-4 cyano groups. In some embodiments, the additive is a combination of a fluorocarbonate and a cyclic carboxylate. In some embodiments, the additive is a combination of fluorocarbonate and cyclic phosphoric anhydride. In some embodiments, the additive is a combination of a fluorocarbonate and a carboxylic acid anhydride. In some embodiments, the additive is a combination of fluorocarbonate and fluorine anhydride. In some embodiments, the additive is a combination of a fluorocarbonate and a carboxylic acid anhydride.
- the electrolyte is not particularly limited, and any known substance as an electrolyte can be arbitrarily used.
- lithium salts are generally used.
- electrolytes may include, but are not limited to, inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAlF 4 , LiSbF 6 , LiTaF 6 , LiWF 7 ; lithium tungstates such as LiWOF 5 ; HCO 2 Li, CH 3 CO 2 Li, CH 2 FCO 2 Li, CHF 2 CO 2 Li, CF 3 CO 2 Li, CF 3 CH 2 CO 2 Li, CF 3 CF 2 CO 2 Li, CF 3 CF 2 CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li and other carboxylate lithium salts; FSO 3 Li, CH 3 SO 3 Li, CH 2 FSO 3 Li, CHF 2 SO 3 Li, CF 3 SO 3 Li, CF 3 CF 2 SO 3 Li, CF
- (malonate) Lithium borate salts tris(malonate) lithium phosphate, difluorobis(malonate) lithium phosphate, tetrafluoro(malonate) lithium phosphate, etc.
- the electrolyte is selected from LiPF6, LiSbF6 , LiTaF6 , FSO3Li , CF3SO3Li , LiN( FSO2 )2 , LiN( FSO2 ) ( CF3SO2 ) , LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , cyclic 1,2-perfluoroethanebissulfonimide lithium, cyclic 1,3-perfluoropropanebissulfonimide lithium, LiC(FSO 2 ) 3 , LiC(CF 3 SO 2 ) 3 , LiC(C 2 F 5 SO 2 ) 3 , LiBF 3 CF 3 , LiBF 3 C 2 F 5 , LiPF 3 (CF 3 ) 3 , LiPF 3 ( C 2 F 5 ) 3 , lithium difluorooxalate borate, lithium bis(oxalate)borate or lithium difluorobis(oxal
- the content of the electrolyte is not particularly limited as long as the effects of the present application are not impaired.
- the total molar concentration of lithium in the electrolyte is greater than 0.3 mol/L, greater than 0.4 mol/L, or greater than 0.5 mol/L.
- the total molar concentration of lithium in the electrolyte is less than 3 mol/L, less than 2.5 mol/L, or less than 2.0 mol/L.
- the total molar concentration of lithium in the electrolyte is within a range consisting of any two of the above-mentioned values. When the electrolyte concentration is within the above-mentioned range, the amount of lithium as the charged particles is not too small, and the viscosity can be kept in an appropriate range, so that it is easy to ensure good electrical conductivity.
- the electrolyte includes at least one salt selected from the group consisting of monofluorophosphate, borate, oxalate, and fluorosulfonate.
- the electrolyte includes a salt selected from the group consisting of monofluorophosphate, oxalate, and fluorosulfonate.
- the electrolyte includes a lithium salt.
- the salt selected from the group consisting of monofluorophosphate, borate, oxalate, and fluorosulfonate is present in an amount greater than 0.01% or greater than 0.1% based on the total weight of the electrolyte.
- the salt selected from the group consisting of monofluorophosphate, borate, oxalate, and fluorosulfonate is present in an amount of less than 20% or less than 10% based on the total weight of the electrolyte. In some embodiments, the amount of salt selected from the group consisting of monofluorophosphates, borates, oxalates, and fluorosulfonates is within a range consisting of any two of the foregoing values.
- the electrolyte comprises one or more species selected from the group consisting of monofluorophosphates, borates, oxalates, and fluorosulfonates, and one or more salts in addition thereto.
- Other salts include the lithium salts exemplified above, and in some examples, LiPF 6 , LiN(FSO 2 )(CF 3 SO 2 ), LiN(CF 3 SO 2 ) 2 , LiN ( C 2 F 5 SO 2 ) 2 , cyclic lithium 1,2-perfluoroethanebissulfonimide, cyclic lithium 1,3-perfluoropropanebissulfonimide, LiC(FSO 2 ) 3 , LiC (CF 3 SO 2 ) 3 , LiC(C 2 F 5 SO 2 ) 3 , LiBF 3 CF 3 , LiBF 3 C 2 F 5 , LiPF 3 (CF 3 ) 3 , LiPF 3 (C 2 F 5 ) 3 .
- the other salts include the lithium salt
- the salts other than these are present in an amount greater than 0.01% or greater than 0.1% based on the total weight of the electrolyte. In some embodiments, the additional salt is present in an amount of less than 20%, less than 15%, or less than 10% based on the total weight of the electrolyte. In some embodiments, the content of other salts is within the range composed of any two of the above-mentioned values. The other salts having the above-mentioned contents help to balance the conductivity and viscosity of the electrolyte.
- the electrolytic solution may contain additional additives such as a negative electrode coating film forming agent, a positive electrode protective agent, and an overcharge inhibitor as necessary.
- additives generally used in non-aqueous electrolyte secondary batteries can be used, and examples thereof can include, but are not limited to, vinylene carbonate, succinic anhydride, biphenyl, cyclohexylbenzene, 2,4-difluorobenzyl Ether, propane sultone, propene sultone, etc. These additives may be used alone or in any combination.
- the content of these additives in the electrolytic solution is not particularly limited, and may be appropriately set according to the type and the like of the additives.
- the additive is present in an amount of less than 5%, in the range of 0.01% to 5%, or in the range of 0.2% to 5%, based on the total weight of the electrolyte.
- the electrochemical device includes an electrode assembly, a current collecting structure, an outer casing and a protective element.
- the electrode assembly may have any of a laminated structure in which the positive electrode and the negative electrode are laminated with the separator layer interposed therebetween, and a wound structure in which the positive electrode and the negative electrode are wound in a spiral shape with the separator layer interposed therebetween.
- the current collecting structure is a structure that reduces the resistance of the wiring portion and the bonding portion.
- the electrode group has the above-described laminated structure, a structure in which the metal core portions of the respective electrode layers are bundled and welded to the terminals is suitably used.
- the electrode area is increased, the internal resistance increases, so it is also suitable to provide two or more terminals in the electrode to reduce the resistance.
- the electrode group has the above-described winding structure, the internal resistance can be reduced by providing two or more lead structures for the positive electrode and the negative electrode, respectively, and bundling them on the terminals.
- the material of the outer casing is not particularly limited as long as it is stable to the electrolyte solution used.
- the outer casing can be used, but not limited to, nickel-plated steel sheet, stainless steel, metal such as aluminum or aluminum alloy, magnesium alloy, or a laminated film of resin and aluminum foil.
- the outer casing is a metal or laminated film of aluminum or aluminum alloy.
- Metal-based outer casings include, but are not limited to, a hermetically sealed structure formed by welding metals to each other by laser welding, resistance welding, or ultrasonic welding, or a riveted structure using the above-mentioned metals through a resin gasket.
- the outer casing using the above-mentioned laminated film includes, but is not limited to, a hermetically sealed structure formed by thermally adhering resin layers to each other, and the like. In order to improve the sealing property, a resin different from the resin used for the laminated film may be interposed between the above-mentioned resin layers.
- a resin having a polar group or a modified resin into which a polar group is introduced can be used as a resin to be sandwiched due to the bonding of the metal and the resin.
- the shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminated type, a button type, a large size, and the like, for example.
- the protective element can use a positive temperature coefficient (PTC), a thermal fuse, a thermistor, whose resistance increases when abnormal heat is generated or an excessive current flows, and can be cut off by rapidly increasing the internal pressure or internal temperature of the battery when abnormal heat is generated A valve (current cutoff valve), etc. for the current flowing in the circuit.
- PTC positive temperature coefficient
- the above-mentioned protective element can be selected to be in a condition that does not work in the normal use of high current, and can also be designed in a form that does not cause abnormal heat release or thermal runaway even if there is no protective element.
- the electrochemical device of the present application includes any device in which an electrochemical reaction occurs, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors.
- the electrochemical device is a lithium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
- the present application further provides an electronic device comprising the electrochemical device according to the present application.
- the use of the electrochemical device of the present application is not particularly limited, and it can be used in any electronic device known in the art.
- the electrochemical devices of the present application may be used in, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets stereo headphones, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power, motors, cars, motorcycles, power Bicycles, bicycles, lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
- FIG. 1 shows a schematic diagram of an embodiment of an electrode assembly of the present application, wherein the electrode assembly includes a positive electrode 1 , a negative electrode 2 , and a separator layer 3 located between the positive electrode 1 and the negative electrode 2 symmetrically arranged with respect to the negative electrode current collector 4 . , polar ear 5.
- the positive electrode 1 includes a positive electrode active layer 11 and a positive electrode conductive layer 12 , wherein the positive electrode conductive layer 12 completely covers the positive electrode active layer 11 .
- the negative electrode includes a negative electrode current collector 4 and a negative electrode active layer 21 disposed on the surface of the negative electrode current collector 4 .
- the separator layer 3 is composed of an inorganic layer and is disposed on the surface of the negative electrode active layer 21 to achieve electrical insulation between the positive electrode 1 and the negative electrode 2 .
- the positive electrode tab 5 is drawn out from the conductive layer 12 .
- FIG. 2 shows a schematic diagram of another embodiment of the electrode assembly of the present application.
- the difference between the structure of the electrode assembly in FIG. 2 and the structure of the electrode assembly in FIG. 1 is that the positive electrode conductive layer 12 is only provided on the surface of the positive electrode active layer 11 , not covering the periphery of the positive electrode active layer 11 , and the electrode of FIG. 2
- the assembly also includes an insulating layer 6 disposed on the surface of the positive conductive layer 12 .
- FIG. 3 shows a schematic diagram of yet another embodiment of the electrode assembly of the present application.
- the difference between the structure of the electrode assembly in FIG. 3 and the structure of the electrode assembly in FIG. 1 is that the separator layer 3 completely covers the negative electrode active layer 21 to prevent short circuit or self-discharge of the battery.
- the artificial graphite, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed with deionized water according to the mass ratio of 96%: 2%: 2%, and stirred evenly to obtain a negative electrode slurry.
- This negative electrode slurry was coated on a 12 ⁇ m copper foil. After drying, cold pressing, cutting and welding the tabs, the negative electrode is obtained.
- the inorganic material ⁇ -AlOOH and the binder PVDF are mixed according to a weight ratio of 80:20, deionized water is added, and the system is stirred under the action of a vacuum mixer until the system becomes a uniform slurry to obtain a coating slurry, wherein the solid content is 40wt%. .
- the surfaces of both sides of the negative electrode are coated with a layer of separator layer slurry as the separator layer.
- the thickness of the separator layer is 15 ⁇ m, and after drying, a negative electrode/separator layer pole piece is obtained.
- the positive active material lithium cobalt oxide (LiCoO 2 ), the conductive agent SP, and the binder polyvinylidene fluoride are mixed according to the weight ratio of 97:1.4:1.6, and N-methylpyrrolidone (NMP) is added.
- NMP N-methylpyrrolidone
- the resulting electrode assembly was wound and placed in an outer wrapping foil, leaving a liquid injection port.
- the electrolyte is poured from the liquid injection port, and the lithium ion battery is prepared through the processes of chemical formation and capacity.
- Steps 1 to 4 are the same as in Example 1, except that the conductive paste is further coated on the surface of the positive electrode, dried to form a conductive layer, and the positive electrode tabs are drawn out from the edge of the conductive layer with conductive glue.
- the conductive paste is composed of a conductive agent and a binder.
- the production method of the conductive paste is as follows:
- the conductive agent and the binder are mixed according to the proportion, N-methylpyrrolidone (NMP) is added, and the conductive paste is prepared after uniform dispersion.
- NMP N-methylpyrrolidone
- the resulting electrode assembly was wound and placed in an outer wrapping foil, leaving a liquid injection port.
- the electrolyte is poured from the liquid injection port, and the lithium ion battery is prepared through the processes of chemical formation and capacity.
- the insulating layer slurry was further coated on the surface of the conductive layer, and dried to form an insulating layer.
- the insulating layer slurry is mixed by a binder and an insulating material according to a proportion, N-methylpyrrolidone (NMP) is added, and the insulating layer slurry is prepared after uniform dispersion.
- NMP N-methylpyrrolidone
- the positive active material lithium cobalt oxide (LiCoO 2 ), the conductive agent SP, and the binder polyvinylidene fluoride are mixed with N-methylpyrrolidone (NMP) according to the mass ratio of 95%: 2%: 3%, and then the auxiliary agent is added. agent, stirring uniformly to obtain a positive electrode slurry.
- the positive electrode slurry was coated on a 12 ⁇ m aluminum foil, dried, cold pressed, and then cut into pieces and welded with tabs to obtain a positive electrode.
- the artificial graphite, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed with deionized water according to the mass ratio of 96%: 2%: 2%, and stirred evenly to obtain a negative electrode slurry.
- This negative electrode slurry was coated on a 12 ⁇ m copper foil. After drying, cold pressing, cutting and welding the tabs, the negative electrode is obtained.
- a polyethylene (PE) porous polymer film was used as the separator.
- the obtained positive electrode, separator and negative electrode were wound in order and placed in an outer packaging foil, leaving a liquid injection port.
- the electrolyte is poured from the liquid injection port, and the lithium ion battery is prepared through the processes of chemical formation and capacity.
- the positive active material lithium cobalt oxide (LiCoO 2 ), the conductive agent SP, and the binder polyvinylidene fluoride are mixed according to the weight ratio of 97:1.4:1.6, and N-methylpyrrolidone (NMP) is added.
- NMP N-methylpyrrolidone
- Under the action of a vacuum mixer Stir until the system becomes a homogeneous slurry to obtain a conventional positive electrode slurry, wherein the solid content of the positive electrode slurry is 72 wt %, and the positive electrode slurry is coated on a 12 ⁇ m aluminum foil. After drying, cold pressing, cutting and welding tabs, the positive electrode is obtained.
- the inorganic material ⁇ -AlOOH and the binder PVDF are mixed according to a weight ratio of 80:20, deionized water is added, and the system is stirred under the action of a vacuum mixer until the system becomes a uniform slurry to obtain a coating slurry, wherein the solid content is 40wt%. .
- the surfaces of both sides of the positive electrode are coated with a layer of separator layer slurry as a separator layer.
- the thickness of the separator layer was 15 ⁇ m, and after drying, the positive electrode/separator layer pole piece was obtained.
- the artificial graphite, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed with deionized water according to the mass ratio of 96%: 2%: 2%, and stirred evenly to obtain a negative electrode slurry.
- the negative electrode slurry is coated on the surface of the separator layer, and after drying, an integrated structure of the negative electrode, the separator layer and the positive electrode is obtained.
- the resulting electrode assembly was wound and placed in an outer wrapping foil, leaving a liquid injection port.
- the electrolyte is poured from the liquid injection port, and the lithium ion battery is prepared through the processes of chemical formation and capacity.
- Table 1 shows the specific structural compositions of Example 1 and Comparative Examples 1-2, as well as the corresponding puncture throughput and energy density.
- Example 1 without the positive electrode current collector Al foil has significantly improved puncture throughput and energy density.
- Comparative Example 2 without the negative electrode current collector copper foil the lithium ion battery using the electrode assembly described in the present application has a higher puncture test pass rate. That is, the lithium ion battery using the electrode assembly described in the present application has higher safety.
- the lithium-ion battery using the electrode assembly described in this application has a higher energy density under the same other conditions.
- the influence of the conductive layer on the performance of the lithium-ion battery is studied below.
- the relevant parameters and test results of the conductive agent, binder, and thickness of the conductive layer in the conductive layer are shown in Table 2.
- Example 2 The results in Table 2 show that, by comparing Examples 2-10 with Example 1, it can be seen that adding a conductive layer can improve the dynamic performance of the cell and improve the rateability of the cell. Examples 10, 14, and 15 with a conductive agent content of 75% have comparable kinetic performance to Comparative Example 1.
- Example 5 On the basis of Example 5 in Table 2, an insulating layer is provided on the surface of the conductive layer. The effects of binders and insulating materials in the insulating layer on the performance of lithium-ion batteries are now investigated. The relevant parameters and test results are shown in Table 3.
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Abstract
本申请提供了一种电极组件,包括负极集流体、设置于所述负极集流体至少一个表面的负极活性层、隔膜层、正极活性层,且所述隔膜层设置于所述负极活性层与所述正极活性层之间,且所述正极活性层的至少部分表面沿垂直于所述部分表面方向的投影区域不存在正极金属集流体。在本申请的电极组件中,不需要金属集流体(例如铝),可以减少整个电极组件的厚度,从而实现更高的能量密度。另外,由于正极不存在金属集流体,可以避免被刺穿时产生金属毛刺刺穿隔膜而导致短路。因此,采用本申请的二次电池(例如锂离子电池)具有更高安全性。
Description
本申请要求于2020年12月04日提交中国专利局、申请号为202011411667.2、申请名称为“一种电极组件及包含其的电化学装置、电子装置”的中国专利的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本申请涉及储能领域,具体涉及一种改善电芯安全性、并提升能量密度的电极组件及包含该电极组件的电化学装置和电子装置。
随着技术的发展和对移动装置的需求的增加,人们对电化学装置(例如,锂离子电池)的需求显著增加。同时具有高安全性、高能量密度的锂离子电池是研究方向之一。
在实际使用中,电化学装置会受到外物的撞击,在极端情况下,会被尖锐的物体所刺穿,当电化学装置被刺穿时,一方面,如果刺穿物为金属体,集流体的刺穿处通过该金属体而与另一电极导通;另一方面,集流体的刺穿处通常会产生毛刺、并随着刺穿物向下变形延伸,从而刺穿隔膜将正极和负极直接连通,导致短路的发生,进而产生大量热量使得电池起火甚至爆炸,严重威胁了消费者的使用安全。同时,消费者对电化学装置的容量及续航时间提出更高的要求。
有鉴于此,确有必要提供改善电芯安全性、并提升能量密度的电极组件及包含其的电化学装置、电子装置。
申请内容
本申请实施例通过提供一种改善电芯安全性、并提升能量密度的电极组件及包含其的电化学装置以在至少某种程度上解决至少一种存在于相关领域中的问题。
在本申请的一方面,本申请提供了一种电极组件,其包括负极集流体、设置于所述负极集流体至少一个表面的负极活性层、隔膜层、正极活性层,所述隔膜层设置于所述负极活性层与所述正极活性层之间,且所述正极活性层的至少部分表面沿垂直于所述部分表面方向的投影区域不存在正极金属集流体。
根据本申请的一些实施方案,所述部分表面占所述正极活性层表面的50%以上,优选80%以上,更优选地95%以上。
在本申请的电极组件中,正极仅包含正极活性层,不需要金属集流体,这种设置可以减少电极组件的整体厚度,提高电极的能量密度。本申请所述的金属集流体,包括铝箔、铜箔、不锈钢箔等由金属材质制成的集流体。
根据本申请的一些实施方案,所述正极活性层与所述隔膜层的粘结力大于或等于2N/m。
根据本申请的一些实施方案,所述正极活性层包括正极活性物质,其中,所述正极活性物质选自锂过渡金属复合氧化物和含锂过渡金属磷酸化合物中的至少一种。
根据本申请的一些实施方案,所述负极活性层包括负极活性物质和粘贴剂,其中,所述负极活性物质选自石墨、硅基材料中的至少一种。
根据本申请的一些实施方案,所述硅基材料选自纯硅、SiOx(0<x<2)、硅碳复合物中的至少一种。
在本申请的电极组件中,负极活性层可以涂覆在负极集流体的一个表面上,也可以涂覆在负极集流体的相背的两个表面上。相应地,在负极集流体的两侧均可以涂覆隔膜层、正极活性物质层和导电层,形成一个相对于负极集流体对称的电极组件。当然,也可以只在一侧涂覆隔膜层、正极活性物质层和导电层。
根据本申请的一些实施方案,所述正极活性层的表面设置有导电层。
根据本申请的一些实施方案,导电层的厚度为0.1μm至30μm。电极组件的厚度与能量密度有密切的关系,导电层不宜过薄,也不宜过厚。导电层的厚度过小,除了增加工艺难度以外,还会导致导电层的厚度不均,造成导电性能不佳。导电层的厚度过大,则会造成整个电极组件厚度过大,最终导致电极组件的能量密度降低。在本申请中,导电层的厚 度为0.1μm至30μm。
电极组件中的导电层包括导电剂,其中,所述导电剂包括炭黑、乙炔黑、富勒烯、碳纳米管、石墨烯、石墨中的至少一种。根据本申请的一些实施方案,所述导电层的表面设置有绝缘层。
根据本申请的一些实施方案,所述绝缘层包括粘结剂,其中基于所述绝缘层的重量,所述粘结剂的质量百分含量为a,其中2%≤a≤100%。在绝缘层中添加粘结剂可以增强绝缘材料之间的粘结性,使绝缘层牢固地粘附在导电层的表面上。在本申请中,粘结剂可以选自聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)、丁腈橡胶、聚胺酯、氟化橡胶、聚乙烯醇(PVA)或聚丙烯酸钠中的至少一种。
根据本申请的一些实施方案,所述绝缘层组成中进一步包括绝缘材料,所述绝缘层厚度h≥0.5μm。
绝缘层中的绝缘材料可以是无机绝缘材料,也可以是有机绝缘材料中的至少一种,或者无机绝缘材料和有机绝缘材料的混合材料。作为示例,无机绝缘材料可以选自BaSO
4、CaSiO
3、γ-AlOOH、CaSiO
4、Al
2O
3、TiO
2中的至少一种,所述有机绝缘材料可以选自乙烯、氯乙烯、丙烯、苯乙烯、丁二烯、偏氟乙烯、四氟乙烯、六氟丙烯的均聚物或共聚物中的至少一种。
根据本申请的一些实施方案,所述绝缘材料的平均粒径为0.01μm至20μm。
根据本申请的一些实施方案,所述隔膜层包括无机层、聚烯烃多孔层中的至少一种。
根据本申请的一些实施方案,所述无机层的组成包括无机颗粒和粘结剂,其中,所述无机颗粒包括BaSO
4、CaSiO
3、γ-AlOOH、CaSiO
4、Al
2O
3、TiO
2、SiO
2中的至少一种。为了保证无机颗粒的粘结性,基于所述无机层的重量,所述粘结剂的含量为b,其中5%≤b≤40%。
根据本申请的一些实施方案,所述负极集流体选自铜箔。铜箔具有优良的稳定性,可以避免在放电时被腐蚀。
根据本申请的一些实施方案,所述电极组件进一步包括极耳。所述极耳为正极极耳,所述正极极耳与正极活性层接触,从而实现正极极耳 与正极活性层的电连接。在另一个实施方案中,所述正极极耳与导电层接触,从而实现极耳与导电层的电连接。
本申请还提供了前述电极组件的制备方法,包括如下步骤:1)依次在所述负极集流体的表面设置所述负极活性层和所述隔膜层;2)在所述隔膜层的表面涂覆所述正极活性层。
根据本申请的一些实施方案,进一步包括步骤:3)在所述正极活性层的表面设置所述导电层或所述绝缘层。
根据本申请的一些实施方案,进一步包括步骤:4)在所述导电层的表面设置所述绝缘层。
本申请还提供一种电化学装置,其包括本发明所述的电极组件。
本申请还提供一种电子装置,包含本申请所述的电化学装置。
本申请的有益效果:
在本申请的电极组件中,正极包括正极活性层和导电层,不需要金属集流体(例如铝),可以减少整个电极组件的厚度,从而实现更高的能量密度。另外,由于正极不存在金属集流体,可以避免被刺穿时产生金属毛刺刺穿隔膜而导致短路。因此,采用本申请的二次电池(例如锂离子电池)具有更高安全性。
为了更清楚地说明本申请的实施方式或现有技术中的技术方案,下面将对实施方式或现有技术描述中所需要使用的附图作简单地介绍。显而易见地,下面描述中的附图仅仅是示例性的,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图引伸获得其它的实施附图。
本说明书所绘示的结构、比例、大小等,均仅用以配合说明书所揭示的内容,以供熟悉此技术的人士了解与阅读,并非用以限定本申请可实施的限定条件,故不具技术上的实质意义,任何结构的修饰、比例关系的改变或大小的调整,在不影响本申请所能产生的功效及所能达成的目的下,均应仍落在本申请所揭示的技术内容得能涵盖的范围内。
图1是本申请电极组件的一种实施方式的示意图;
图2是本申请电极组件的另一种实施方式的示意图;
图3是本申请电极组件的又一种实施方式的示意图。
附图标记:
1-正极
11-正极活性层
12-正极导电层
2-负极
21-负极活性层
3-隔膜层
4-负极集流体
5-正极极耳
6-绝缘层。
本申请的实施例将会被详细的描示在下文中。本申请的实施例不应该被解释为对本申请的限制。
除非另外明确指明,本文使用的下述术语具有下文指出的含义。
在具体实施方式及权利要求书中,由术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如,如果列出项目A及B,那么短语“A及B中的至少一者”意味着仅A;仅B;或A及B。在另一实例中,如果列出项目A、B及C,那么短语“A、B及C中的至少一者”意味着仅A;或仅B;仅C;A及B(排除C);A及C(排除B);B及C(排除A);或A、B及C的全部。项目A可包含单个元件或多个元件。项目B可包含单个元件或多个元件。项目C可包含单个元件或多个元件。
电化学装置(例如,锂离子电池)的电极(正极或负极)通常通过以下方法制备:将活性材料、导电剂、增稠剂、粘结剂和溶剂混合,然后将混合后的浆料涂布于集流体上。然而,当电化学装置被刺穿时,一方面,如果刺穿物为金属体,集流体的刺穿处通过该金属体而与另一电极导通;另一方面,集流体的刺穿处通常会产生毛刺、并随着刺穿物向下变形延伸,从而刺穿隔膜将正负极直接连通,导致短路的发生。
本申请通过使用特定结构的电极组件结构,取消了传统的正极集流体Al箔,避免了电化学装置在穿钉过程中,高延展性的金属集流体Al箔随着穿刺物延伸而与另一电极的接触,同时,也避免了金属毛刺的产生,从而刺穿隔离膜造成短路,改善了电化学装置的安全性。同时,在电化学装置中取消非活性的金属集流体也大大提升了能量密度。
在一个实施例中,本申请提供了一种电化学装置,其包括如下所述负极、正极和隔膜层的电极组件以及电解液。
I、负极
负极包括负极集流体和设置在所述负极集流体的一个或两个表面上的负极活性层。
负极活性层可以是一层或多层,多层负极活性层中的每层可以包含相同或不同的负极活性物质。负极活性物质为任何能够可逆地嵌入和脱嵌锂离子等金属离子的物质。在一些实施例中,负极活性层的可充电容量大于正极活性层的放电容量,以防止在充电期间锂金属无意地析出在负极上。
作为保持负极活性物质的集流体,可以任意使用公知的集流体。负极集流体的实例包括,但不限于,铝、铜、镍、不锈钢、镀镍钢等金属材料。在一些实施例中,负极集流体为铜。
在负极集流体为金属材料的情况下,负极集流体形式可包括,但不限于,金属箔、金属圆柱、金属带卷、金属板、金属薄膜、金属板网、冲压金属、发泡金属等。在一些实施例中,负极集流体为金属薄膜。在一些实施例中,负极集流体为铜箔。在一些实施例中,负极集流体为基于压延法的压延铜箔或基于电解法的电解铜箔。
在一些实施例中,负极集流体的厚度为大于1μm或大于5μm。在一些实施例中,负极集流体的厚度为小于100μm或小于50μm。在一些实施例中,负极集流体的厚度在上述任意两个数值所组成的范围内。
负极活性物质没有特别限制,只要能够可逆地吸藏、放出锂离子即可。负极活性物质的实例可包括,但不限于,天然石墨、人造石墨等碳材料;纯硅(Si)、氧化亚硅、硅碳复合物、硅与金属元素的合金等硅基材料。负极活性物质可以单独使用或组合使用。
负极活性层还可包括负极粘合剂。负极粘合剂可提高负极活性物质 颗粒彼此间的结合和负极活性物质与集流体的结合。负极粘合剂的种类没有特别限制,只要是对于电解液或电极制造时使用的溶剂稳定的材料即可。在一些实施例中,负极粘合剂包括树脂粘合剂。树脂粘合剂的实例包括,但不限于,氟树脂、聚丙烯腈(PAN)、聚酰亚胺树脂、丙烯酸系树脂、聚烯烃树脂等。当使用水系溶剂制备负极合剂浆料时,负极粘合剂包括,但不限于,羧甲基纤维素(CMC)或其盐、苯乙烯-丁二烯橡胶(SBR)、聚丙烯酸(PAA)或其盐、聚乙烯醇等。
负极可以通过以下方法制备:在负极集流体上涂布包含负极活性物质、树脂粘结剂等的负极合剂浆料,干燥后,进行压延而在负极集流体的两面形成负极活性层,由此可以得到负极。
II、正极
正极包括正极活性层,可进一步在正极活性层的表面设置导电层。根据本申请的一些实施方案,还可进一步在所述导电层的表面设置绝缘层。
1、正极活性层
正极活性层包含正极活性物质。正极活性层可以是一层或多层,多层正极活性层中的每层可以包含相同或不同的正极活性物质。正极活性物质为任何能够可逆地嵌入和脱嵌锂离子等金属离子的物质。在一些实施例中,正极活性层的放电容量小于负极活性层的可充电容量,以防止在充电期间锂金属无意地析出在负极上。
(1)正极活性物质
正极活性物质的种类没有特别限制,只要是能够以电化学方式吸藏和释放金属离子(例如,锂离子)即可。在一些实施例中,正极活性物质为含有锂和至少一种过渡金属的物质。正极活性物质的实例可包括,但不限于,锂过渡金属复合氧化物和含锂过渡金属磷酸化合物。
在一些实施例中,锂过渡金属复合氧化物中的过渡金属包括V、Ti、Cr、Mn、Fe、Co、Ni、Cu等。在一些实施例中,锂过渡金属复合氧化物包括LiCoO
2等锂钴复合氧化物;LiNiO
2等锂镍复合氧化物;LiMnO
2、LiMn
2O
4、Li
2MnO
4等锂锰复合氧化物;LiNi
1/3Mn
1/3Co
1/3O
2、LiNi
0.5Mn
0.3Co
0.2O
2等锂镍锰钴复合氧化物,其中作为这些锂过渡金属复合氧化物的主体的过渡金属原子的一部分被Na、K、B、F、Al、Ti、V、 Cr、Mn、Fe、Co、Li、Ni、Cu、Zn、Mg、Ga、Zr、Si、Nb、Mo、Sn、W等其它元素所取代。锂过渡金属复合氧化物的实例可包括,但不限于,LiNi
0.5Mn
0.5O
2、LiNi
0.85Co
0.10Al
0.05O
2、LiNi
0.33Co
0.33Mn
0.33O
2、LiNi
0.45Co
0.10Al
0.45O
2、LiMn
1.8Al
0.2O
4和LiMn
1.5Ni
0.5O
4等。锂过渡金属复合氧化物的组合的实例包括,但不限于,LiCoO
2与LiMn
2O
4的组合,其中LiMn
2O
4中的一部分Mn可被过渡金属所取代(例如,LiNi
0.33Co
0.33Mn
0.33O
2),LiCoO
2中的一部分Co可被过渡金属所取代。
在一些实施例中,含锂过渡金属磷酸化合物中的过渡金属包括V、Ti、Cr、Mn、Fe、Co、Ni、Cu等。在一些实施例中,含锂过渡金属磷酸化合物包括LiFePO
4、Li
3Fe
2(PO
4)
3、LiFeP
2O
7等磷酸铁类、LiCoPO
4等磷酸钴类,其中作为这些锂过渡金属磷酸化合物的主体的过渡金属原子的一部分被Al、Ti、V、Cr、Mn、Fe、Co、Li、Ni、Cu、Zn、Mg、Ga、Zr、Nb、Si等其它元素所取代。
在一些实施例中,使用锂过渡金属氧化物Li
aM
bO
2的粉末状材料,其中0.9≤a≤1.1,0.9≤b≤1.1,且M主要是选自Mn、Co和Ni的过渡金属,其中,组成M随粒度改变。
在一些实施例中,在锂过渡金属氧化物Li
aM
bO
2的粉末状的电极活性材料中,其中M=A
ZA’
Z’M’
1-Z-Z’,M’=Mn
xNi
yCo
1-x-y,0≤y≤1,0≤x≤1,0≤Z+Z’≤0.1,Z’≤0.02,A选自元素Al、Mg、Ti、Cr中至少一种,且A’选自元素F、Cl、S、Zr、Ba、Y、Ca、B、Be、Sn、Sb、Na、Zn中的至少一种。
在一些实施例中,所述过渡金属平均组成是M=Mn
xNi
yCo
1-x-y,其中0.03≤x≤0.35。
在一些实施例中,所述过渡金属平均组成是M=Mn
xNi
yCo
1-x-y,其中0.03≤x,且x+y≤0.7。
在一些实施例中,在具有组成与尺寸相关的Li
aM
bO
2的粉末状的电极活性材料中,基本上所有颗粒的所有部分具有层状晶体结构,较大颗粒具有组成Li
aM
bO
2,其中M=Mn
xNi
yCo
1-x-y,x+y≤0.35,小颗粒具有组成Li
aM
bO
2,其中M=Mn
x’Ni
y’Co
1-x’-y’,其具有至少低10%的Co,(1-x’-y’)≤0.9×(1-x-y),以及至少高5%的Mn,x’-x>0.05。由此,可以获得具有组成与尺寸相关的粉末,也即一种成分具有大的颗粒(例如分布集中在≥20 μm);其成分能够快速体相扩散。另一种成分具有小的颗粒(例如分布于5μm周围)且其成分能确保安全性。从而提供将高循环稳定性和高安全性与高体积能量密度和高重量能量密度结合起来的电极活性材料。
在一些实施例中,所述正极活性材料具有宽的粒度分布,其规定为大颗粒与小颗粒的粒度比大于3,Dv90/Dv10>3,其中,Dv90表示在体积基准的粒度分布中,从小粒径侧起、达到体积累积90%的粒径。Dv10表示在体积基准的粒度分布中,从小粒径侧起、达到体积累积10%的粒径。粉末的粒度分布可以通过现有技术中已知的适当方法测定。适当的方法例如激光衍射或通过使用具有不同目数的套筛进行筛分。
在一些实施例中,单个颗粒基本上是锂过渡金属氧化物,且单个颗粒具有Co,其在过渡金属中的含量随粒度连续提高。
在一些实施例中,单个颗粒在过渡金属中还含有Mn,且Mn含量随粒度连续降低。
在一些实施例中,大颗粒具有能获得高Li扩散常数的接近于LiCoO
2组成的大颗粒,因此能获得足够的速率性能。大颗粒仅占正极的总表面积的小部分。因此,由在表面或在外侧部分与电解质反应放出的热量得到限制;结果,大的颗粒较少导致差的安全性。小颗粒具有含有较少Co的组成以获得提高的安全性。较低的锂扩散常数在小颗粒中可以被接受而没有明显的速率性能的损失,这是由于固态扩散路径的长度短。
在一些实施例中,小颗粒的优选组成含有较少量的Co和较大量的稳定元素,如Mn。较缓慢的Li体扩散可以被接受,但表面的稳定性高。在本发明的阴极活性材料粉末中,大颗粒的优选组成含有较大量的Co和较少量的Mn,这是由于需要快速的锂体扩散,而表面稍低的稳定性可以被接受。
在一些实施例中,在组成为Li
xMO
2的单个颗粒的内部中,优选至少80w%的M是钴或镍。在一些实施例中,颗粒的内侧部分具有接近于LiCoO
2的组成。外侧部分是锂锰镍钴氧化物。
制备具有组成与尺寸相关的粉末状的电极活性材料可以通过如下方法:将至少一种含有过渡金属的沉淀物沉积在晶种颗粒上,所述晶种颗粒具有与沉淀物不同的过渡金属组成;添加控制量的锂源;并进行至少一种热处理,其中基本上所有获得的颗粒含有得自晶种的内核,该内核 完全被得自沉淀物的层覆盖。
2、导电层
导电层将正极的电流导通并至少部分地覆盖在正极的至少一个表面上。
根据本申请的一些实施例,所述导电层厚度为0.1μm至30μm。
根据本申请的一些实施例,所述导电层包括导电剂,所述导电剂包括炭黑、乙炔黑、富勒烯、碳纳米管、石墨烯、石墨中的至少一种。
3、绝缘层
为了避免导电层与穿刺物接触,避免穿钉时发生短路,在导电层的表面设置绝缘层。
根据本申请的一些实施例,所述绝缘层包括粘结剂。
根据本申请的一些实施例,所述绝缘层进一步包括绝缘材料。
根据本申请的一些实施例,基于所述绝缘层的重量,所述粘结剂的质量百分含量为a,其中2%≤a≤100%,绝缘材料的质量百分含量为1-a。
根据本申请的一些实施例,所述绝缘材料包括无机绝缘材料和/或有机绝缘材料中的至少一种。
根据本申请的一些实施例,所述无机绝缘材料包括BaSO
4、CaSiO
3、γ-AlOOH、CaSiO
4、Al
2O
3、TiO
2中的至少一种;所述有机绝缘材料包括乙烯、氯乙烯、丙烯、苯乙烯、丁二烯、偏氟乙烯、四氟乙烯、六氟丙烯的均聚物或共聚物中的至少一种。
根据本申请的一些实施例,所述绝缘材料的颗粒度D50为0.01μm至20μm,优选0.5μm至5μm。绝缘材料的颗粒度在这个范围内时,可以保证绝缘材料在层中的分散均匀性,以及保证绝缘层涂层的厚度。
根据本申请的一些实施例,所述绝缘层厚度h≥0.5μm。
根据本申请的一些实施例,所述粘结剂包括聚偏氟乙烯PVDF、聚四氟乙烯PTFE、羧甲基纤维素钠CMC、丁苯橡胶SBR、丁腈橡胶、聚胺酯、氟化橡胶、聚乙烯醇PVA、聚丙烯酸钠中的至少一种。
III、隔膜层
为了防止短路,在正极与负极之间设置有隔膜层。
隔膜层可通过现有已知方式设置在正极与负极之间。例如,在电极的表面涂覆浆料成型,或者通过在电极的表面进行静电纺丝,或者通过 常规堆叠的方式将预先制备好的隔离膜与正负极进行堆叠。
例如,在电极的表面涂覆浆料成型时,所述隔膜层包括无机颗粒和粘结剂,所述粘结剂选自聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)、丁腈橡胶、聚胺酯、氟化橡胶、聚乙烯醇(PVA)、聚丙烯酸钠中的至少一种。
根据本申请的一些实施方案,所述无机颗粒包括BaSO
4、CaSiO
3、γ-AlOOH、CaSiO
4、Al
2O
3、TiO
2、SiO
2中的至少一种。
根据本申请的一些实施方案,所述无机颗粒的颗粒度D50为0.01μm至20μm,优选0.5μm至5μm。
隔膜层的厚度是任意的。在一些实施例中,所述隔膜层的厚度为大于1μm、大于5μm或大于8μm。在一些实施例中,所述隔膜层的厚度为小于50μm、小于40μm或小于30μm。在一些实施例中,所述隔膜层的厚度在上述任意两个数值所组成的范围内。当所述隔膜层的厚度在上述范围内时,则可以确保绝缘性和机械强度,并可以确保电化学装置的倍率特性和能量密度。
在使用多孔性膜片或无纺布等多孔质材料作为隔膜层时,隔膜层的孔隙率是任意的。在一些实施例中,所述隔膜层的孔隙率为大于20%、大于35%或大于45%。在一些实施例中,所述隔膜层的孔隙率为小于90%、小于85%或小于75%。在一些实施例中,所述隔膜层的孔隙率在上述任意两个数值所组成的范围内。当所述隔膜层的孔隙率在上述范围内时,可以确保绝缘性和机械强度,并可以抑制膜电阻,使电化学装置具有良好的倍率特性。
隔膜层的平均孔径也是任意的。在一些实施例中,所述隔膜层的平均孔径为小于0.5μm或小于0.2μm。在一些实施例中,所述隔膜层的平均孔径为大于0.05μm。在一些实施例中,所述隔膜层的平均孔径在上述任意两个数值所组成的范围内。若所述隔膜层的平均孔径超过上述范围,则容易发生短路。当隔膜层的平均孔径在上述范围内时,在防止短路的同时可抑制了膜电阻,使电化学装置具有良好的倍率特性。
IV、电解液
对于液态二次电池,本申请的电化学装置中的使用的电解液包括电解质和溶解该电解质的溶剂。在一些实施例中,本申请的电化学装置中 的使用的电解液进一步包括添加剂。
在一些实施例中,所述电解液进一步包含现有技术中已知的任何可作为电解液的溶剂的非水溶剂。
在一些实施例中,所述非水溶剂包括,但不限于,以下中的一种或多种:环状碳酸酯、链状碳酸酯、环状羧酸酯、链状羧酸酯、环状醚、链状醚、含磷有机溶剂、含硫有机溶剂和芳香族含氟溶剂。
在一些实施例中,所述环状碳酸酯的实例可包括,但不限于,以下中的一种或多种:碳酸亚乙酯(EC)、碳酸亚丙酯(PC)和碳酸亚丁酯。在一些实施例中,所述环状碳酸酯具有3-6个碳原子。
在一些实施例中,所述链状碳酸酯的实例可包括,但不限于,以下中的一种或多种:碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯(DEC)、碳酸甲基正丙基酯、碳酸乙基正丙基酯、碳酸二正丙酯等链状碳酸酯等。被氟取代的链状碳酸酯的实例可包括,但不限于,以下中的一种或多种:双(氟甲基)碳酸酯、双(二氟甲基)碳酸酯、双(三氟甲基)碳酸酯、双(2-氟乙基)碳酸酯、双(2,2-二氟乙基)碳酸酯、双(2,2,2-三氟乙基)碳酸酯、2-氟乙基甲基碳酸酯、2,2-二氟乙基甲基碳酸酯和2,2,2-三氟乙基甲基碳酸酯等。
在一些实施例中,所述环状羧酸酯的实例可包括,但不限于,以下中的一种或多种:γ-丁内酯和γ-戊内酯中的一种或多种。在一些实施例中,环状羧酸酯的部分氢原子可被氟取代。
在一些实施例中,所述链状羧酸酯的实例可包括,但不限于,以下中的一种或多种:乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸异丙酯、乙酸丁酯、乙酸仲丁酯、乙酸异丁酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸异丙酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、异丁酸甲酯、异丁酸乙酯、戊酸甲酯、戊酸乙酯、特戊酸甲酯和特戊酸乙酯等。在一些实施例中,链状羧酸酯的部分氢原子可被氟取代。在一些实施例中,氟取代的链状羧酸酯的实例可包括,但不限于,三氟乙酸甲酯、三氟乙酸乙酯、三氟乙酸丙酯、三氟乙酸丁酯和三氟乙酸2,2,2-三氟乙酯等。
在一些实施例中,所述环状醚的实例可包括,但不限于,以下中的一种或多种:四氢呋喃、2-甲基四氢呋喃、1,3-二氧戊环、2-甲基1,3-二氧戊环、4-甲基1,3-二氧戊环、1,3-二氧六环、1,4-二氧六环和二甲氧基丙 烷。
在一些实施例中,所述链状醚的实例可包括,但不限于,以下中的一种或多种:二甲氧基甲烷、1,1-二甲氧基乙烷、1,2-二甲氧基乙烷、二乙氧基甲烷、1,1-二乙氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基甲烷、1,1-乙氧基甲氧基乙烷和1,2-乙氧基甲氧基乙烷等。
在一些实施例中,所述含磷有机溶剂的实例可包括,但不限于,以下中的一种或多种:磷酸三甲酯、磷酸三乙酯、磷酸二甲基乙酯、磷酸甲基二乙酯、磷酸亚乙基甲酯、磷酸亚乙基乙酯、磷酸三苯酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三苯酯、磷酸三(2,2,2-三氟乙基)酯和磷酸三(2,2,3,3,3-五氟丙基)酯等。
在一些实施例中,所述含硫有机溶剂的实例可包括,但不限于,以下中的一种或多种:环丁砜、2-甲基环丁砜、3-甲基环丁砜、二甲基砜、二乙基砜、乙基甲基砜、甲基丙基砜、二甲基亚砜、甲磺酸甲酯、甲磺酸乙酯、乙磺酸甲酯、乙磺酸乙酯、硫酸二甲酯、硫酸二乙酯和硫酸二丁酯。在一些实施例中,含硫有机溶剂的部分氢原子可被氟取代。
在一些实施例中,所述芳香族含氟溶剂包括,但不限于,以下中的一种或多种:氟苯、二氟苯、三氟苯、四氟苯、五氟苯、六氟苯和三氟甲基苯。
在一些实施例中,本申请的电解液中使用的溶剂包括环状碳酸酯、链状碳酸酯、环状羧酸酯、链状羧酸酯及其组合。在一些实施例中,本申请的电解液中使用的溶剂包括碳酸亚乙酯、碳酸亚丙酯、碳酸二乙酯、丙酸乙酯、丙酸丙酯、乙酸正丙酯、或乙酸乙酯中的至少一种。在一些实施例中,本申请的电解液中使用的溶剂包含:碳酸亚乙酯、碳酸亚丙酯、碳酸二乙酯、丙酸乙酯、丙酸丙酯、γ-丁内酯及其组合。
在电解液中加入链状羧酸酯及/或环状羧酸酯后,链状羧酸酯及/或环状羧酸酯可在电极表面形成钝化膜,从而提高电化学装置的间歇充电循环后的容量保持率。在一些实施例中,所述电解液中含有1%至60%的链状羧酸酯、环状羧酸酯及其组合。在一些实施例中,所述电解液中含有丙酸乙酯、丙酸丙酯、γ-丁内酯及其组合,基于电解液的总重量,该组合的含量为1%至60%、10%至60%、10%至50%、20%至50%。在一些实施例中,基于电解液的总重量,所述电解液中含有1%至60%、10%至60%、 20%至50%、20%至40%或30%的丙酸丙酯。
在一些实施例中,所述添加剂的实例可包括,但不限于,以下的一种或多种:氟代碳酸酯、含碳碳双键的碳酸乙烯酯、含硫氧双键的化合物和酸酐。
在一些实施例中,基于所述电解液的总重量,所述添加剂的含量为0.01%至15%、0.1%至10%或1%至5%。
根据本申请的实施例,基于所述电解液的总重量,所述丙酸酯的含量为所述添加剂的1.5至30倍、1.5至20倍、2至20倍或5-20倍。
在一些实施例中,所述添加剂包含一种或多种氟代碳酸酯。在锂离子电池充电/放电时,氟代碳酸酯可与丙酸酯共同作用以在负极的表面上形成稳定的保护膜,从而抑制电解液的分解反应。
在一些实施例中,所述氟代碳酸酯具有式C=O(OR
1)(OR
2),其中R
1和R
2各自选自具有1-6个碳原子的烷基或卤代烷基,其中R
1和R
2中的至少一者选自具有1-6个碳原子的氟代烷基,且R
1和R
2任选地连同其所连接的原子形成5元至7元环。
在一些实施例中,所述氟代碳酸酯的实例可包括,但不限于,以下的一种或多种:氟代碳酸乙烯酯、顺式4,4-二氟碳酸乙烯酯、反式4,4-二氟碳酸乙烯酯、4,5-二氟碳酸乙烯酯、4-氟-4-甲基碳酸乙烯酯、4-氟-5-甲基碳酸乙烯酯、碳酸三氟甲基甲酯、碳酸三氟乙基甲酯和碳酸乙基三氟乙酯等。
在一些实施例中,所述添加剂包含一种或多种含碳碳双键的碳酸乙烯酯。所述含碳碳双键的碳酸乙烯酯的实例可包括,但不限于,以下的一种或多种:碳酸亚乙烯酯、碳酸甲基亚乙烯酯、碳酸乙基亚乙烯酯、碳酸-1,2-二甲基亚乙烯酯、碳酸-1,2-二乙基亚乙烯酯、碳酸氟亚乙烯酯、碳酸三氟甲基亚乙烯酯;碳酸乙烯基亚乙酯、碳酸-1-甲基-2-乙烯基亚乙酯、碳酸-1-乙基-2-乙烯基亚乙酯、碳酸-1-正丙基-2-乙烯基亚乙酯、碳酸1-甲基-2-乙烯基亚乙酯、碳酸-1,1-二乙烯基亚乙酯、碳酸-1,2-二乙烯基亚乙酯、碳酸-1,1-二甲基-2-亚甲基亚乙酯和碳酸-1,1-二乙基-2-亚甲基亚乙酯等。在一些实施例中,所述含碳碳双键的碳酸乙烯酯包括碳酸亚乙烯酯,其易于获得并可实现更为优异的效果。
在一些实施例中,所述添加剂包含一种或多种含硫氧双键的化合物。 所述含硫氧双键的化合物的实例可包括,但不限于,以下的一种或多种:环状硫酸酯、链状硫酸酯、链状磺酸酯、环状磺酸酯、链状亚硫酸酯和环状亚硫酸酯等。
所述环状硫酸酯的实例可包括,但不限于,以下的一种或多种:1,2-乙二醇硫酸酯、1,2-丙二醇硫酸酯、1,3-丙二醇硫酸酯、1,2-丁二醇硫酸酯、1,3-丁二醇硫酸酯、1,4-丁二醇硫酸酯、1,2-戊二醇硫酸酯、1,3-戊二醇硫酸酯、1,4-戊二醇硫酸酯和1,5-戊二醇硫酸酯等。
所述链状硫酸酯的实例可包括,但不限于,以下的一种或多种:硫酸二甲酯、硫酸甲乙酯和硫酸二乙酯等。
所述链状磺酸酯的实例可包括,但不限于,以下的一种或多种:氟磺酸甲酯和氟磺酸乙酯等氟磺酸酯、甲磺酸甲酯、甲磺酸乙酯、二甲磺酸丁酯、2-(甲磺酰氧基)丙酸甲酯和2-(甲磺酰氧基)丙酸乙酯等。
所述环状磺酸酯的实例可包括,但不限于,以下的一种或多种:1,3-丙磺酸内酯、1-氟-1,3-丙磺酸内酯、2-氟-1,3-丙磺酸内酯、3-氟-1,3-丙磺酸内酯、1-甲基-1,3-丙磺酸内酯、2-甲基-1,3-丙磺酸内酯、3-甲基-1,3-丙磺酸内酯、1-丙烯-1,3-磺酸内酯、2-丙烯-1,3-磺酸内酯、1-氟-1-丙烯-1,3-磺酸内酯、2-氟-1-丙烯-1,3-磺酸内酯、3-氟-1-丙烯-1,3-磺酸内酯、1-氟-2-丙烯-1,3-磺酸内酯、2-氟-2-丙烯-1,3-磺酸内酯、3-氟-2-丙烯-1,3-磺酸内酯、1-甲基-1-丙烯-1,3-磺酸内酯、2-甲基-1-丙烯-1,3-磺酸内酯、3-甲基-1-丙烯-1,3-磺酸内酯、1-甲基-2-丙烯-1,3-磺酸内酯、2-甲基-2-丙烯-1,3-磺酸内酯、3-甲基-2-丙烯-1,3-磺酸内酯、1,4-丁磺酸内酯、1,5-戊磺酸内酯、甲烷二磺酸亚甲酯和甲烷二磺酸亚乙酯等。
链状亚硫酸酯的实例可包括,但不限于,以下的一种或多种:亚硫酸二甲酯、亚硫酸甲乙酯和亚硫酸二乙酯等。
环状亚硫酸酯的实例可包括,但不限于,以下的一种或多种:1,2-乙二醇亚硫酸酯、1,2-丙二醇亚硫酸酯、1,3-丙二醇亚硫酸酯、1,2-丁二醇亚硫酸酯、1,3-丁二醇亚硫酸酯、1,4-丁二醇亚硫酸酯、1,2-戊二醇亚硫酸酯、1,3-戊二醇亚硫酸酯、1,4-戊二醇亚硫酸酯和1,5-戊二醇亚硫酸酯等。
在一些实施例中,所述添加剂包含一种或多种酸酐。所述酸酐的实例可包括,但不限于,环状磷酸酐、羧酸酐、二磺酸酐和羧酸磺酸酐中的一种或多种。所述环状磷酸酐的实例可包括,但不限于,三甲基磷酸 环酐、三乙基磷酸环酐和三丙基磷酸环酐中的一种或多种。所述羧酸酐的实例可包括,但不限于,琥珀酸酐、戊二酸酐和马来酸酐中的一种或多种。所述二磺酸酐的实例可包括,但不限于,乙烷二磺酸酐和丙烷二磺酸酐中的一种或多种。所述羧酸磺酸酐的实例可包括,但不限于,磺基苯甲酸酐、磺基丙酸酐和磺基丁酸酐中的一种或多种。
在一些实施例中,所述添加剂为氟代碳酸酯与含碳碳双键的碳酸乙烯酯的组合。在一些实施例中,所述添加剂为氟代碳酸酯与含硫氧双键的化合物的组合。在一些实施例中,所述添加剂为氟代碳酸酯与具有2-4个氰基的化合物的组合。在一些实施例中,所述添加剂为氟代碳酸酯与环状羧酸酯的组合。在一些实施例中,所述添加剂为氟代碳酸酯与环状磷酸酐的组合。在一些实施例中,所述添加剂为氟代碳酸酯与羧酸酐的组合。在一些实施例中,所述添加剂为氟代碳酸酯与璜酸酐的组合。在一些实施例中,所述添加剂为氟代碳酸酯与羧酸璜酸酐的组合。
在本申请中,对电解质没有特别限制,可以任意地使用作为电解质公知的物质。在锂二次电池的情况下,通常使用锂盐。电解质的实例可包括,但不限于,LiPF
6、LiBF
4、LiClO
4、LiAlF
4、LiSbF
6、LiTaF
6、LiWF
7等无机锂盐;LiWOF
5等钨酸锂类;HCO
2Li、CH
3CO
2Li、CH
2FCO
2Li、CHF
2CO
2Li、CF
3CO
2Li、CF
3CH
2CO
2Li、CF
3CF
2CO
2Li、CF
3CF
2CF
2CO
2Li、CF
3CF
2CF
2CF
2CO
2Li等羧酸锂盐类;FSO
3Li、CH
3SO
3Li、CH
2FSO
3Li、CHF
2SO
3Li、CF
3SO
3Li、CF
3CF
2SO
3Li、CF
3CF
2CF
2SO
3Li、CF
3CF
2CF
2CF
2SO
3Li等磺酸锂盐类;LiN(FCO)
2、LiN(FCO)(FSO
2)、LiN(FSO
2)
2、LiN(FSO
2)(CF
3SO
2)、LiN(CF
3SO
2)
2、LiN(C
2F
5SO
2)
2、环状1,2-全氟乙烷双磺酰亚胺锂、环状1,3-全氟丙烷双磺酰亚胺锂、LiN(CF
3SO
2)(C
4F
9SO
2)等酰亚胺锂盐类;LiC(FSO
2)
3、LiC(CF
3SO
2)
3、LiC(C
2F
5SO
2)
3等甲基化锂盐类;双(丙二酸根合)硼酸锂盐、二氟(丙二酸根合)硼酸锂盐等(丙二酸根合)硼酸锂盐类;三(丙二酸根合)磷酸锂、二氟双(丙二酸根合)磷酸锂、四氟(丙二酸根合)磷酸锂等(丙二酸根合)磷酸锂盐类;以及LiPF
4(CF
3)
2、LiPF
4(C
2F
5)
2、LiPF
4(CF
3SO
2)
2、LiPF
4(C
2F
5SO
2)
2、LiBF
3CF
3、LiBF
3C
2F
5、LiBF
3C
3F
7、LiBF
2(CF
3)2、LiBF
2(C
2F
5)
2、LiBF
2(CF
3SO
2)
2、LiBF
2(C
2F
5SO
2)
2等含氟有机锂盐类;二氟草酸硼酸锂、双(草酸)硼酸锂等草酸硼酸锂盐类;四氟草酸根合磷酸锂、二氟双(草酸 根合)磷酸锂、三(草酸根合)磷酸锂等草酸根合磷酸锂盐类等。
在一些实施例中,电解质选自LiPF
6、LiSbF
6、LiTaF
6、FSO
3Li、CF
3SO
3Li、LiN(FSO
2)
2、LiN(FSO
2)(CF
3SO
2)、LiN(CF
3SO
2)
2、LiN(C
2F
5SO
2)
2、环状1,2-全氟乙烷双磺酰亚胺锂、环状1,3-全氟丙烷双磺酰亚胺锂、LiC(FSO
2)
3、LiC(CF
3SO
2)
3、LiC(C
2F
5SO
2)
3、LiBF
3CF
3、LiBF
3C
2F
5、LiPF
3(CF
3)
3、LiPF
3(C
2F
5)
3、二氟草酸硼酸锂、双(草酸)硼酸锂或二氟双(草酸根合)磷酸锂,其有助于改善电化学装置的输出功率特性、高倍率充放电特性、高温保存特性和循环特性等。
电解质的含量没有特别限制,只要不损害本申请的效果即可。在一些实施例中,电解液中的锂的总摩尔浓度为大于0.3mol/L以上、大于0.4mol/L或大于0.5mol/L。在一些实施例中,电解液中的锂的总摩尔浓度为小于3mol/L、小于2.5mol/L或小于2.0mol/L以下。在一些实施例中,电解液中的锂的总摩尔浓度在上述任意两个数值所组成的范围内。当电解质浓度在上述范围内时,作为带电粒子的锂不会过少,并且可以使粘度处于适当的范围,因而容易确保良好的电导率。
当使用两种以上的电解质的情况下,电解质包括至少一种为选自由单氟磷酸盐、硼酸盐、草酸盐和氟磺酸盐组成的组中的盐。在一些实施例中,电解质包括选自由单氟磷酸盐、草酸盐和氟磺酸盐组成的组中的盐。在一些实施例中,电解质包括锂盐。在一些实施例中,基于电解质的总重量,选自由单氟磷酸盐、硼酸盐、草酸盐和氟磺酸盐组成的组中的盐的含量为大于0.01%或大于0.1%。在一些实施例中,基于电解质的总重量,选自由单氟磷酸盐、硼酸盐、草酸盐和氟磺酸盐组成的组中的盐的含量为小于20%或小于10%。在一些实施例中,选自由单氟磷酸盐、硼酸盐、草酸盐和氟磺酸盐组成的组中的盐的含量在上述任意两个数值所组成的范围内。
在一些实施例中,电解质包含选自由单氟磷酸盐、硼酸盐、草酸盐和氟磺酸盐组成的组中的一种以上物质和除此以外的一种以上的盐。作为除此以外的盐,可以举出在上文中例示的锂盐,在一些实施例中为LiPF
6、LiN(FSO
2)(CF
3SO
2)、LiN(CF
3SO
2)
2、LiN(C
2F
5SO
2)
2、环状1,2-全氟乙烷双磺酰亚胺锂、环状1,3-全氟丙烷双磺酰亚胺锂、LiC(FSO
2)
3、LiC(CF
3SO
2)
3、LiC(C
2F
5SO
2)
3、LiBF
3CF
3、LiBF
3C
2F
5、LiPF
3(CF
3)
3、 LiPF
3(C
2F
5)
3。在一些实施例中,除此以外的盐为LiPF
6。
在一些实施例中,基于电解质的总重量,除此以外的盐的含量为大于0.01%或大于0.1%。在一些实施例中,基于电解质的总重量,除此以外的盐的含量为小于20%、小于15%或小于10%。在一些实施例中,除此以外的盐的含量在上述任意两个数值所组成的范围内。具有上述含量的除此以外的盐有助于平衡电解液的电导率和粘度。
在电解液中,除了含有上述溶剂、添加剂和电解质盐以外,可以根据需要含有负极被膜形成剂、正极保护剂、防过充电剂等额外添加剂。作为添加剂,可使用一般在非水电解质二次电池中使用的添加剂,其实例可包括,但不限于,碳酸亚乙烯酯、琥珀酸酐、联苯、环己基苯、2,4-二氟苯甲醚、丙烷磺内酯、丙烯磺内酯等。这些添加剂可以单独使用或任意组合使用。另外,电解液中的这些添加剂的含量没有特别限制,可以根据该添加剂的种类等适当地设定即可。在一些实施例中,基于电解液的总重量,添加剂的含量为小于5%、在0.01%至5%的范围内或在0.2%至5%的范围内。
V、电化学装置
电化学装置包括电极组件、集电结构、外装壳体和保护元件。
电极组件
电极组件可以是由上述正极和负极隔着上述隔膜层层积而成的层积结构、以及上述正极和负极隔着上述隔膜层以漩涡状卷绕而成的卷绕结构中的任一种。
集电结构
对集电结构没有特别限制。在一些实施例中,集电结构为降低配线部分及接合部分的电阻的结构。当电极组为上述层积结构时,适合使用将各电极层的金属芯部分捆成束而焊接至端子上所形成的结构。电极面积增大时,内部电阻增大,因而在电极内设置2个以上的端子而降低电阻也是适合使用的。当电极组为上述卷绕结构时,通过在正极和负极分别设置2个以上的引线结构,并在端子上捆成束,从而可以降低内部电阻。
外装壳体
外装壳体的材质没有特别限制,只要是对于所使用的电解液稳定的 物质即可。外装壳体可使用,但不限于,镀镍钢板、不锈钢、铝或铝合金、镁合金等金属类、或者树脂与铝箔的层积膜。在一些实施例中,外装壳体为铝或铝合金的金属或层积膜。
金属类的外装壳体包括,但不限于,通过激光焊接、电阻焊接、超声波焊接将金属彼此熔敷而形成的封装密闭结构;或者隔着树脂制垫片使用上述金属类形成的铆接结构。使用上述层积膜的外装壳体包括,但不限于,通过将树脂层彼此热粘而形成的封装密闭结构等。为了提高密封性,还可以在上述树脂层之间夹入与层积膜中所用的树脂不同的树脂。在通过集电端子将树脂层热粘而形成密闭结构时,由于金属与树脂的接合,可使用具有极性基团的树脂或导入了极性基团的改性树脂作为夹入的树脂。另外,外装体的形状也是任意的,例如可以为圆筒形、方形、层积型、纽扣型、大型等中的任一种。
保护元件
保护元件可以使用在异常放热或过大电流流过时电阻增大的正温度系数(PTC)、温度熔断器、热敏电阻、在异常放热时通过使电池内部压力或内部温度急剧上升而切断在电路中流过的电流的阀(电流切断阀)等。上述保护元件可选择在高电流的常规使用中不工作的条件的元件,亦可设计成即使不存在保护元件也不至于发生异常放热或热失控的形式。
VI、应用
本申请的电化学装置包括发生电化学反应的任何装置,它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。特别地,该电化学装置是锂二次电池,包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
本申请另提供了一种电子装置,其包括根据本申请的电化学装置。
本申请的电化学装置的用途没有特别限定,其可用于现有技术中已知的任何电子装置。在一些实施例中,本申请的电化学装置可用于,但不限于,笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用 电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
下面以锂离子电池为例并且结合具体的实施例说明包括本申请所述的电极组件的锂离子电池的制备,本领域的技术人员将理解,本申请中描述的制备方法仅是实例,其他任何合适的制备方法均在本申请的范围内。
图1示出了本申请的电极组件的一种实施例的示意图,其中,电极组件包括相对于负极集流体4对称设置的正极1、负极2、位于正极1与负极2之间的隔膜层3、极耳5。
正极1包括正极活性层11和正极导电层12,其中,正极导电层12将正极活性层11完全包覆。负极包括负极集流体4和设置在负极集流体4表面的负极活性层21。隔膜层3由无机层构成,设置在负极活性层21的表面上,实现正极1与负极2之间的电绝缘。在导电层12上引出正极极耳5。
图2示出了本申请的电极组件的另一种实施例的示意图。图2中的电极组件的结构与图1中的电极组件的结构的区别在于:正极导电层12仅设置在正极活性层11的表面上,未覆盖正极活性层11的周边,并且图2的电极组件还包括设置在正极导电层12的表面上的绝缘层6。
图3示出了本申请的电极组件的又一种实施例的示意图。图3中的电极组件的结构与图1中的电极组件的结构的区别在于:隔膜层3完全包覆负极活性层21,以防止电池的短路或自放电。
实施例
以下就包括本申请的电极组件的锂离子电池的实施例和对比例进行性能评估。
一、锂离子电池的制备
实施例1
1、负极的制备
将人造石墨、丁苯橡胶和羧甲基纤维素钠按照96%:2%:2%的质量比例与去离子水混合,搅拌均匀,得到负极浆料。将该负极浆料涂布在12μm的铜箔上。干燥,冷压,再经过裁片、焊接极耳,得到负极。
2、隔膜层浆料的制备
将无机材料γ-AlOOH、粘结剂PVDF按照重量比80∶20进行混合,加入去离子水,在真空搅拌机作用下搅拌至体系成均一浆料,获得涂层浆料,其中固含量为40wt%。
3、负极/隔膜层极片的制备
负极两侧表面涂覆一层隔膜层浆料作为隔膜层。隔膜层的厚度为15μm,经过干燥后,得到负极/隔膜层极片。
4、电极组件的制备
将正极活性材料钴酸锂(LiCoO
2)、导电剂SP、粘结剂聚偏二氟乙烯按照重量比97∶1.4∶1.6进行混合,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌至体系成均一浆料,获得常规正极浆料,其中正极浆料的固含量为72wt%;正极浆料涂覆在隔膜层表面,经过干燥后,得到负极、隔膜层和正极一体结构。
5、用导电胶在正极边缘引出正极极耳。
6、锂离子电池的制备
将得到的电极组件卷绕,置于外包装箔中,留下注液口。从注液口灌注电解液,封装,再经过化成、容量等工序制得锂离子电池。
实施例2至实施例15
步骤1至步骤4与实施例1相同,区别在于:进一步将导电浆料涂覆在正极表面,烘干形成导电层,并用导电胶在导电层边缘引出正极极耳。
导电浆料由导电剂和粘结剂组成,导电浆料的制作方法如下:
将导电剂和粘结剂按配比混合,加入N-甲基吡咯烷酮(NMP),分散均匀后制得导电浆料。
锂离子电池的制备
将得到的电极组件卷绕,置于外包装箔中,留下注液口。从注液口灌注电解液,封装,再经过化成、容量等工序制得锂离子电池。
实施例1至实施例15的锂离子电池的相关参数见表2。
实施例16至实施例25
在实施例5的基础上,进一步将绝缘层浆料涂覆在导电层表面,烘干形成绝缘层。
绝缘层浆料由粘结剂和绝缘材料按配比混合,加入N-甲基吡咯烷酮(NMP),分散均匀后制得绝缘层浆料。
实施例16至实施例25的锂离子电池的相关参数见表3。
对比例1
1、正极的制备
将正极活性材料钴酸锂(LiCoO
2)、导电剂SP、粘结剂聚偏二氟乙烯按照95%∶2%∶3%的质量比例与N-甲基吡咯烷酮(NMP)混合,再加入助剂,搅拌均匀,得到正极浆料。将该正极浆料涂布在12μm的铝箔上,干燥,冷压,再经过裁片、焊接极耳,得到正极。
2、负极的制备
将人造石墨、丁苯橡胶和羧甲基纤维素钠按照96%∶2%∶2%的质量比例与去离子水混合,搅拌均匀,得到负极浆料。将该负极浆料涂布在12μm的铜箔上。干燥,冷压,再经过裁片、焊接极耳,得到负极。
3、电解液的制备
在干燥氩气环境下,将EC、PC、PP和DEC(重量比1∶1∶1∶1)混合,加入LiPF
6混合均匀,形成基础电解液,其中LiPF
6的浓度为1.15mol/L。
4、隔离膜的制备
以聚乙烯(PE)多孔聚合物薄膜作为隔离膜。
5、锂离子电池的制备
将得到的正极、隔离膜和负极按次序卷绕,置于外包装箔中,留下注液口。从注液口灌注电解液,封装,再经过化成、容量等工序制得锂离子电池。
对比例2
1、正极的制备
将正极活性材料钴酸锂(LiCoO
2)、导电剂SP、粘结剂聚偏二氟乙烯按照重量比97∶1.4∶1.6进行混合,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌至体系成均一浆料,获得常规正极浆料,其中正极浆料的固含量为72wt%,将该正极浆料涂布在12μm的铝箔上。干燥,冷压,再经过裁片、焊接极耳,得到正极。
2、隔膜层浆料的制备
将无机材料γ-AlOOH、粘结剂PVDF按照重量比80∶20进行混合,加入去离子水,在真空搅拌机作用下搅拌至体系成均一浆料,获得涂层浆料,其中固含量为40wt%。
3、正极/隔膜层极片
正极两侧表面涂覆一层隔膜层浆料作为隔膜层。隔膜层的厚度为15μm,经过干燥后,得到正极/隔膜层极片。
4、电极组件的制备
将人造石墨、丁苯橡胶和羧甲基纤维素钠按照96%:2%:2%的质量比例与去离子水混合,搅拌均匀,得到负极浆料。负极浆料涂覆在隔膜层表面,经过干燥后,得到负极、隔膜层和正极一体结构。
5、用导电胶在负极边缘引出负极极耳。
6、锂离子电池的制备
将得到的电极组件卷绕,置于外包装箔中,留下注液口。从注液口灌注电解液,封装,再经过化成、容量等工序制得锂离子电池。
二、测试方法
1、穿刺试验通过率的测试方法
取10组相同电极组件制得的电芯,0.5C CC至满充电压,CV至0.05C;温度20±5℃,钉子直径4mm,穿刺速度30mm/s,保留300s;以电芯不起火、不爆炸视为通过测试,将通过测试的电芯数n/测试电芯总数10定义为穿刺试验通过率。
2、能量密度测试方法
0.5C CC至满充电压,CV至0.05C,0.5C DC至3.0V,记录放电容量能量密度=放电容量/(长度*宽度*厚度)
三、测试结果
表1展示了实施例1和对比例1-2的具体结构组成以及相应的穿刺通过率和能量密度。
表1
由表1的结果表明,通过实施例与对比例1比较可知,取消正极集流体Al箔的实施例1具有显著提升的穿刺通过率和能量密度。相比于没有负极集流体铜箔的对比例2,采用本申请所述的电极组件的锂离子电池具有更高的穿刺试验通过率。即,采用本申请所述的电极组件的锂离子电池具有更高的安全性。另外,由于不需要使用正极集流体,因此,在其他条件相同的情况下,采用本申请所述的电极组件的锂离子电池具有更高的能量密度。
下面就导电层对锂离子电池性能的影响进行研究,导电层中的导电剂、粘结剂、导电层的厚度等相关参数和测试结果见表2。
表2
表2的结果表明,通过实施例2-10与实施例1比较可知,增加导电层可以提升电芯动力学性能,改善电芯倍率性。导电剂含量为75%的实施例10、14、15与对比例1具有相当的动力学性能。
在表2中的实施例5的基础上,在导电层的表面设置一层绝缘层。现在就绝缘层中的粘结剂和绝缘材料对锂离子电池性能的影响进行研究。相关参数和测试结果见表3。
表3
表3的结果表明,在导电层表面进一步设置绝缘层的实施例具有提升的穿刺通过率,这是由于绝缘层的存在能够避免金属穿刺物与导电层的接触,从而避免导电层通过金属刺穿物与负极连通,造成短路和热失控,进而大大提高了电化学装置的安全性能。
尽管已经演示和描述了说明性实施例,本领域技术人员应该理解上述实施例不能被解释为对本申请的限制,并且可以在不脱离本申请的精神、原理及范围的情况下对实施例进行改变,替代和修改。
Claims (10)
- 一种电极组件,其包括负极集流体、设置于所述负极集流体至少一个表面的负极活性层、隔膜层、正极活性层,所述隔膜层设置于所述负极活性层与所述正极活性层之间,且所述正极活性层的至少部分表面沿垂直于所述部分表面方向的投影区域不存在正极金属集流体。
- 根据权利要求1所述的电极组件,所述正极活性层的表面设置有导电层。
- 根据权利要求2所述的电极组件,所述导电层包括导电剂,其满足以下条件的至少一者:a.所述导电层厚度为0.1μm至30μm;b.所述导电剂包括炭黑、乙炔黑、富勒烯、碳纳米管、石墨烯、石墨中的至少一种。
- 根据权利要求2所述的电极组件,所述导电层的表面设置有绝缘层。
- 根据权利要求4所述的电极组件,所述绝缘层包括粘结剂,其满足以下条件的至少一者:c.所述绝缘层包括绝缘材料;d.基于所述绝缘层的重量,所述粘结剂的质量百分含量为a,其中,2%≤a≤100%;e.所述绝缘层厚度h≥0.5μm。
- 根据权利要求5所述的电极组件,所述绝缘材料包括无机绝缘材料和/或有机绝缘材料中的至少一种,其满足以下条件的至少一者:f.所述无机绝缘材料包括BaSO 4、CaSiO 3、γ-AlOOH、CaSiO 4、Al 2O 3、TiO 2中的至少一种;所述有机绝缘材料包括乙烯、氯乙烯、丙烯、苯乙烯、丁二烯、偏氟乙烯、四氟乙烯、六氟丙烯的均聚物或共聚物中的至少一种;g.所述绝缘材料的平均粒径为0.01μm至20μm。
- 根据权利要求1所述的电极组件,所述电极组件满足以下条件的至少一者:h.所述电极组件进一步包括极耳,所述极耳与所述导电层连接;i.所述隔膜层包括无机层、聚烯烃多孔层中的至少一种;j.所述负极活性层包括负极活性物质,所述负极活性物质包括石墨、硅基材料中的至少一种;k.所述部分表面占所述正极活性层表面的50%以上,优选80%以上,更优选地95%以上;l.所述正极活性层与所述隔膜层的粘结力大于或等于2N/m。
- 根据权利要求7所述的电极组件,所述无机层的组成包括无机颗粒和粘结剂,其满足以下条件的至少一者:m.基于所述无机层的重量,所述粘结剂的质量百分含量为b,其中5%≤b≤40%;n.所述无机颗粒包括BaSO 4、CaSiO 3、γ-AlOOH、CaSiO 4、Al 2O 3、TiO 2、SiO 2中的至少一种;o.所述无机颗粒的D50为0.01μm至20μm;p.所述粘结剂包括聚偏氟乙烯、聚四氟乙烯、羧甲基纤维素钠、丁苯橡胶、丁腈橡胶、聚胺酯、氟化橡胶、聚乙烯醇或聚丙烯酸钠中的至少一种。
- 一种电化学装置,其包括权利要求1至8任一项所述的电极组件。
- 一种电子装置,包含权利要求9所述的电化学装置。
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