CN110600680A - Positive electrode slurry, positive plate comprising positive electrode slurry and lithium ion battery - Google Patents
Positive electrode slurry, positive plate comprising positive electrode slurry and lithium ion battery Download PDFInfo
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- CN110600680A CN110600680A CN201910708655.7A CN201910708655A CN110600680A CN 110600680 A CN110600680 A CN 110600680A CN 201910708655 A CN201910708655 A CN 201910708655A CN 110600680 A CN110600680 A CN 110600680A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000011267 electrode slurry Substances 0.000 title claims description 13
- 239000000463 material Substances 0.000 claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000006258 conductive agent Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000006257 cathode slurry Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000006256 anode slurry Substances 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910008722 Li2NiO2 Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides anode slurry, an anode plate comprising the anode slurry and a lithium ion battery, wherein the anode slurry comprises an anode active main material, a pre-lithium functional material, a conductive agent and a binder; the positive active main material, the pre-lithium functional material, the conductive agent and the binder are mixed according to the following weight parts: 77-97 parts of positive active main material, 0-15 parts of pre-lithium functional material, 0.1-3 parts of conductive agent and 1-5 parts of binder; the chemical formula of the pre-lithium functional material is LixMyNz. According to the anode slurry, the anode plate comprising the anode slurry and the lithium ion battery, the gram capacity of the anode active main material can be effectively improved by reasonably matching the anode active main material with the pre-lithium functional material with low coulombic efficiency, so that the capacity of the lithium ion battery can be improved, and the anode slurry has operability and universality.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of lithium ion batteries, and particularly relates to anode slurry, an anode plate comprising the anode slurry, and a lithium ion battery.
[ background of the invention ]
The lithium ion secondary battery has the characteristics of high specific energy, long cycle life, low self-discharge, no memory effect and the like, and in recent years, along with the gradual deterioration of atmospheric environment and ecological environment, the environmental awareness of people is continuously improved, and the lithium ion secondary battery is gradually widely applied to the fields of automobiles, energy storage and the like.
In general, a compound capable of reversibly intercalating and deintercalating lithium ions is selected as a positive and negative electrode active material for a lithium ion secondary battery, and the battery capacity and cycle life are determined by the amount of reversibly deintercalating lithium ions. As is well known, the first coulombic efficiency of a lithium ion battery is determined by the lower first efficiency of the positive and negative electrode materials. When the first effect of the high-nickel material serving as the positive electrode is 88% and the first effect of the graphite negative electrode is 92%, the first coulombic efficiency of the lithium ion secondary battery is 86-87%, namely the first effect of the battery core is determined by the high-nickel positive electrode. When negative active materials such as high-capacity silicon alloy and the like are introduced into the manufacturing process of the negative electrode of the lithium ion battery, the first coulombic efficiency of the secondary battery is restricted by the low first effect of the high-silicon material, so that the actual capacity exertion of the positive electrode in the manufacturing process of the high-energy-density battery cell is too low, and the capacity loss of the positive active material is caused.
In addition to the disclosed electrochemical lithium supplementing manner, for the first irreversible loss of the battery cell, an active lithium source is usually added manually, and a lithium sheet, lithium powder or lithium salt consistent with the first irreversible capacity loss is added into the battery cell to supplement the active lithium capacity in the battery cell, but the above manner can cause direct exposure of the active lithium or the defect of complex lithium supplementing process, and thus, the safety is difficult to guarantee. Namely, the lithium supplementing method adopted in the prior art has certain problems in the aspects of operability, universality, utilization rate and actual effect, can not well compensate for active lithium consumed by first irreversible capacity loss, and has great limitation in the aspect of improving the energy density of a battery cell.
[ summary of the invention ]
The technical problem to be solved by the invention is as follows: aiming at various limitations existing in the process of improving the energy density of a battery cell in the prior art by a lithium supplementing mode, the invention provides the anode slurry, the anode plate comprising the anode slurry and the lithium ion battery, which can well improve the energy density of the battery cell and can also avoid the problems of difficult operation, poor safety and low utilization rate existing in the lithium supplementing mode in the prior art.
The present invention provides a positive electrode slurry, including: the lithium ion battery comprises a positive active main material, a pre-lithium functional material, a conductive agent and a binder; the positive active main material, the pre-lithium functional material, the conductive agent and the binder are mixed according to the following weight parts: 77-97 parts of positive active main material, 0-15 parts of pre-lithium functional material, 0.1-3 parts of conductive agent and 1-5 parts of binder.
In a preferred embodiment, the positive active main material is one or two of a nickel-cobalt-manganese ternary material NCM, a nickel-cobalt-manganese ternary material NCA, a lithium cobaltate LCO, lithium-rich manganese and high-voltage lithium nickel manganese.
In a preferred embodiment, the chemical formula of the pre-lithium functional material is LixMyNz, wherein x is more than or equal to 1 and less than or equal to 8, y is more than or equal to 0 and less than or equal to 6, and z is more than or equal to 1 and less than or equal to 6; m is one or more metal elements of Fe, Cu, Mn, Zr, Mg and Al; n is one or more non-metallic elements of O, N, F, B and S.
In a preferred embodiment, the binder includes, but is not limited to, one or more of polyvinyl alcohol, polyurethane, polyacrylate, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, epoxy, neoprene.
In a preferred embodiment, the pre-lithium functional material adopts sacrificial lithium salt with coulombic efficiency (0-40%), or lithium compound with coulombic efficiency (30-80%) or lithium-rich compound with coulombic efficiency (60-90%).
In a preferred embodiment, the pre-lithium functional material has a decomposition voltage in the range of (0.5-5) V.
The invention also provides a positive plate using the positive slurry, which comprises a positive current collector and a positive slurry layer positioned on the positive current collector, wherein the positive slurry layer is formed by coating the positive slurry on the positive current collector.
In a preferred embodiment, the positive electrode current collector is a porous aluminum foil or a porous copper foil, in particular a porous pole piece compacted by 3.0-3.5, and the porosity is designed to be 10-40%.
In a preferred embodiment, the manufacturing environment of the positive plate is properly controlled below 5% RH, and the slurry mixing mode is performed under the protection of argon at normal pressure or under vacuum negative pressure.
The present invention provides a lithium ion battery using the positive electrode sheet, including: the lithium battery comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the positive plate is the positive plate.
The invention has the following beneficial effects: according to the anode slurry, the anode plate comprising the anode slurry and the lithium ion battery, the gram capacity of the anode active main material can be effectively improved by reasonably matching the anode active main material with the pre-lithium functional material with low coulombic efficiency, so that the capacity of the lithium ion battery can be improved, and the anode slurry has operability and universality.
[ description of the drawings ]
FIG. 1 is a first charge-discharge curve diagram of a positive electrode sheet in example 1 of the present invention and a positive electrode sheet in comparative example 1;
fig. 2 is a graph of lithium ion capacity retention rate versus cycle number using the lithium ion battery in example 2 and the lithium ion battery in comparative example 2.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantageous effects of the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The positive electrode slurry comprises a positive electrode active main material, a pre-lithium functional material, a conductive agent and a binder; the positive active main material, the pre-lithium functional material, the conductive agent and the binder are mixed according to the following weight parts: 77-97 parts of positive active main material, 0-15 parts of pre-lithium functional material, 0.1-3 parts of conductive agent and 1-5 parts of binder;
the positive active main material is preferably one or two of a nickel-cobalt-manganese ternary material NCM, a nickel-cobalt-manganese ternary material NCA, lithium cobaltate LCO, lithium-rich manganese and high-voltage lithium nickel manganese oxide.
The chemical formula of the pre-lithium functional material is LixMyNz, wherein x is more than or equal to 1 and less than or equal to 8, y is more than or equal to 0 and less than or equal to 6, and z is more than or equal to 1 and less than or equal to 6; m is one or more metal elements of Fe, Cu, Mn, Zr, Mg and Al; n is one or more non-metallic elements of O, N, F, B and S;
the binder includes, but is not limited to, polyvinyl alcohol, polyurethane, polyacrylate, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, epoxy resin, neoprene and other high molecular compounds.
Through research, the lithium pre-functional material in the invention is beneficial to improving the energy density of the battery by adopting the sacrificial lithium salt with the coulombic efficiency (0-40%), and secondly, the lithium pre-functional material can also adopt the over-lithium compound with the coulombic efficiency (30-80%) and the lithium-rich compound with the coulombic efficiency (60-90%).
Preferably, the decomposition voltage of the pre-lithium functional material is in the range of (0.5-5) V, and preferably, the decomposition voltage is in the range of (2-3.7) V, which contributes to the improvement of the energy density of the battery.
The invention also provides a positive plate using the positive slurry, which comprises a positive current collector and a positive slurry layer positioned on the positive current collector, wherein the positive slurry layer is formed by coating the positive slurry provided by the invention on the positive current collector.
The positive current collector can adopt an aluminum foil or a copper foil, and can be selected according to actual needs.
The preferable positive electrode current collector is a porous aluminum foil or a porous copper foil, particularly a porous pole piece which is compacted by 3.0-3.5 is preferable, and the porosity is designed to be 10-40%; alternatively a light foil. And the thickness thereof is preferably 9 μm or 12 μm or 16 μm.
Preferably, the manufacturing environment of the positive electrode sheet is controlled to be appropriately less than or equal to 5% RH, and the slurry mixing method is preferably performed under normal pressure argon protection or vacuum negative pressure.
According to the invention, by reasonably matching the positive active main material and the pre-lithium functional material with low coulombic efficiency, the gram capacity of the positive active main material can be effectively improved, and further the capacity of the lithium ion battery can be improved.
The invention also provides a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the positive plate is the positive plate provided by the application, and the positive plate can adopt a conventional positive plate in the prior art;
the negative electrode active material used by the negative electrode is preferably one of silicon, silicon alloy and other high-capacity lithium intercalation materials, wherein the gram capacity of the negative electrode piece is preferably between 360-650, and the negative electrode capacity/positive electrode capacity is required to be 1.0-1.3; for example, the SIO content of the silicon negative electrode material can be selected to be within 0-20%, the first effect of the silicon negative electrode is between 90% and 75%, and the first effect of the battery cell is 1% to 2% lower than that of the silicon negative electrode.
The dry method and wet method base membrane or ceramic with the membrane thickness of 6-20 microns, and the PVDF coated membrane is excellent
Adding a conventional lithium salt or a functional lithium salt into the electrolyte;
the solvent may be a conventional solvent and a functional additive.
The advantages of the positive electrode sheet in the present invention are further described below by comparing example 1 with comparative example 1:
example 1, a manufacturing process of a positive electrode sheet of the present invention:
the positive electrode active main material NCM811 (specific capacity of 195mAh/g), the pre-lithium functional material Li2NiO2, the conductive agent SP + CNT and the binder PVDF are mixed according to the weight ratio of 89.2%: 5.8%: 1.8%: 2.2 percent of the positive plate is weighed, homogenized by a wet homogenization process, coated on a carbon-coated positive current collector aluminum foil, the thickness of the aluminum foil is 12um, the thickness of a carbon-coated layer is 1um, the coating surface density is 380g/m2(N/P is 15 percent), meanwhile, slurry is sampled and inspected to perform half-cell test, the semi-cell test is performed on the slurry, the slurry is dried and then rolled to form a roller, the compaction density is 3.42g/cm3, and the positive plate is obtained by.
Comparative example 1, comparative example 1 is a manufacturing process of a positive electrode sheet to which a pre-lithium functional material is not added:
a positive electrode active main material NCM811 (specific capacity of 195mAh/g), a conductive agent SP + CNT and a binder PVDF are mixed according to the weight ratio of 96%: 1.8%: 2.2 percent of the slurry is weighed, homogenized by a wet homogenization process, coated on a carbon-coated aluminum foil, the thickness of the aluminum foil is 12um, the thickness of a carbon-coated layer is 1um, the coating surface density is 380g/m2(N/P is 15 percent), meanwhile, the slurry is sampled and inspected to carry out a half-cell test, and the slurry is dried and then is rolled to form a roll, and the compaction density is 3.42g/cm 3. And (4) splitting and die cutting to obtain the positive plate of the comparative example 1.
The positive electrode sheet in the embodiment 1 and the positive electrode sheet in the comparative example 1 are subjected to a charge and discharge test to obtain a first charge and discharge curve as shown in fig. 1, and as can be seen from fig. 1, a specific capacity curve of the positive electrode sheet in the embodiment 1 is longer than that of the comparative example 1 in the charging process, and a specific capacity curve of the positive electrode sheet in the embodiment 1 is shorter than that of the comparative example 1 in the discharging process, so that the positive electrode sheet in the invention is more beneficial to improving the energy of the lithium ion battery.
The advantages of the lithium ion battery using the positive electrode sheet in the present invention are further described below by comparing example 2 with comparative example 2:
embodiment 2 is a process of manufacturing a lithium ion battery using the positive electrode sheet of the present invention:
the positive electrode active main material NCM811 (specific capacity of 195mAh/g), the pre-lithium functional material Li2NiO2, the conductive agent SP + CNT and the binder PVDF are mixed according to the weight ratio of 87.5%: 8.5%: 1.5%: weighing 2.5 percent, adopting a wet homogenization process, firstly adding PVDF (polyvinylidene fluoride) as a binder and NMP (N-methyl pyrrolidone) as a solvent into a stirrer according to the weight ratio of 1:10, stirring for 3 hours until the PVDF is fully dissolved, then adding SP + CNT (styrene-butadiene-styrene) as a conductive agent, stirring for 1 hour, finally adding dried main positive electrode material and Li2NiO2 as a pre-lithium active material, stirring for 3 hours, adjusting the viscosity by using NMP, and controlling the viscosity range to be 6500 and 8500 mPa.s. And (3) coating the uniformly dispersed slurry on a carbon-coated aluminum foil with the thickness of 12 mu m, the thickness of a carbon-coated layer of 1 mu m and the coating surface density of 380g/m2(N/P is 15%), drying, and then compacting by a roller to obtain the density of 3.42g/cm 3. Splitting and die cutting to obtain a positive plate;
laminating the positive plate and a silicon negative plate with the designed capacity of 450 and the coated surface density of 220g/m2, assembling, forming and grading the battery to obtain the lithium ion battery, and performing corresponding electrical property test and key tracking cycle performance on the lithium ion battery;
comparative example 2, a process for making lithium ions in the prior art:
a positive electrode active main material NCM811 (specific capacity of 195mAh/g), a conductive agent SP + CNT and a binder PVDF are mixed according to the weight ratio of 96%: 1.5%: weighing 2.5 percent, adopting a wet homogenization process, firstly adding PVDF (polyvinylidene fluoride) as a binder and NMP (N-methyl pyrrolidone) as a solvent into a stirrer according to the weight ratio of 1:10, stirring for 3 hours until the PVDF is fully dissolved, then adding SP + CNT (styrene-butadiene-styrene) as a conductive agent, stirring for 1 hour, finally adding the dried main material of the positive electrode, stirring for 3 hours, adjusting the viscosity by using NMP, and controlling the viscosity range to be 6500 and 8500 mPa.s. And (3) coating the uniformly dispersed slurry on a carbon-coated aluminum foil with the thickness of 12 mu m, the thickness of a carbon-coated layer of 1 mu m and the coating surface density of 380g/m2(N/P is 15%), drying, and then compacting by a roller to obtain the density of 3.42g/cm 3. Splitting and die cutting to obtain a positive plate;
and (3) laminating the positive plate and a silicon negative plate with the designed capacity of 450 and the coated surface density of 220g/m2, assembling, forming and grading the battery to obtain the conventional lithium ion battery, and performing corresponding electrical property test and focusing on tracking cycle performance.
Corresponding electrical property tests are carried out on the high-energy-density lithium ion battery disclosed by the invention in the embodiment 2 and the lithium ion battery in the comparative example 2, a capacity retention rate-cycle frequency curve diagram in fig. 2 is obtained by focusing on tracking cycle performance, and as can be seen from fig. 2, under the same cycle frequency, the capacity retention rate of the high-energy-density lithium ion battery in the embodiment 2 is obviously higher than that of a common lithium ion battery.
The analysis shows that the positive electrode slurry provided by the invention is beneficial to improving the energy density of the lithium ion battery, and has better operability and universality.
The positive electrode slurry of the present invention and the positive electrode sheet and the lithium ion battery including the same are not limited only to those described in the specification and the embodiments, and thus additional advantages and modifications will be readily apparent to those skilled in the art, and the present invention is not limited to specific details, representative devices, and illustrative examples shown and described herein, without departing from the spirit and scope of the general concept as defined by the appended claims and their equivalents.
Claims (10)
1. The positive electrode slurry is characterized by comprising a positive electrode active main material, a pre-lithium functional material, a conductive agent and a binder; the positive active main material, the pre-lithium functional material, the conductive agent and the binder are mixed according to the following weight parts: 77-97 parts of positive active main material, 0-15 parts of pre-lithium functional material, 0.1-3 parts of conductive agent and 1-5 parts of binder.
2. The positive electrode slurry according to claim 1, wherein the positive electrode active main material is one or two of a nickel-cobalt-manganese ternary material NCM, a nickel-cobalt-manganese ternary material NCA, a lithium cobaltate LCO, a lithium-rich manganese, and a high-voltage lithium nickel manganese oxide.
3. The positive electrode slurry according to claim 1, wherein the chemical formula of the pre-lithium functional material is LixMyNz, wherein 1. ltoreq. x.ltoreq.8, 0. ltoreq. y.ltoreq.6, 1. ltoreq. z.ltoreq.6; m is one or more metal elements of Fe, Cu, Mn, Zr, Mg and Al; n is one or more non-metallic elements of O, N, F, B and S.
4. The positive electrode slurry according to claim 1, wherein the binder comprises but is not limited to one or more of polyvinyl alcohol, polyurethane, polyacrylate, polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, epoxy resin, and chloroprene rubber.
5. The positive electrode slurry according to claim 1, wherein the pre-lithium functional material is a sacrificial lithium salt having a coulombic efficiency (0-40%), or a superlithium compound having a coulombic efficiency (30-80%) or a lithium-rich compound having a coulombic efficiency (60-90%).
6. The cathode slurry according to claim 1, wherein the pre-lithium functional material has a decomposition voltage in the range of (0.5-5) V.
7. A positive plate, comprising a positive current collector and a positive slurry layer on the positive current collector, wherein the positive slurry layer is formed by coating the positive slurry according to any one of claims 1 to 6 on the positive current collector.
8. The positive plate according to claim 7, wherein the positive electrode current collector is a porous aluminum foil or a porous copper foil, specifically a porous plate compacted by 3.0-3.5, and has a porosity designed at 10-40%.
9. The positive electrode sheet according to claim 7, wherein the production environment of the positive electrode sheet is appropriately controlled to 5% RH or less, and the slurry mixing method is performed under normal pressure argon gas protection or vacuum negative pressure.
10. A lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet, a separator, an electrolyte and a case, wherein the positive electrode sheet is the positive electrode sheet according to any one of claims 7 to 9.
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