CN115275181B - Lithium ion battery and battery pack - Google Patents
Lithium ion battery and battery pack Download PDFInfo
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- CN115275181B CN115275181B CN202210683772.4A CN202210683772A CN115275181B CN 115275181 B CN115275181 B CN 115275181B CN 202210683772 A CN202210683772 A CN 202210683772A CN 115275181 B CN115275181 B CN 115275181B
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- active material
- electrode active
- ion battery
- positive electrode
- lithium ion
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 51
- 239000007774 positive electrode material Substances 0.000 claims abstract description 49
- 229910052796 boron Inorganic materials 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000011149 active material Substances 0.000 claims abstract description 20
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 30
- -1 methylene methylsulfonate Chemical compound 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 3
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 3
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
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- 238000003860 storage Methods 0.000 abstract description 29
- 229910052710 silicon Inorganic materials 0.000 description 12
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- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
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- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 230000037427 ion transport Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- 229940017219 methyl propionate Drugs 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Abstract
The invention provides a lithium ion battery and a battery pack, which comprises electrolyte, a battery cell and a shell for containing the electrolyte and the battery cell, wherein after the lithium ion battery is charged and discharged, a solid electrolyte interface film is formed on the surface of a positive electrode active material layer, at least the solid electrolyte interface film comprises sulfur element and boron element, the weight ratio of the sum of the sulfur element and the boron element to the sum of the weights of the positive electrode active material layer and the solid electrolyte interface film is k, and the unit is wt%; taking the conductivity of the electrolyte as d, and the unit is mS/cm; the positive electrode active material layer has a compacted density ρ in g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The weight percentage of nickel element in the lithium nickel-based active material is r, and r is 20 to 60 weight percent; the following relationship is satisfied: and (100. D. K. Rho/r) is less than or equal to 0.3 and less than or equal to 45. Compared with the existing nickel-based positive electrode battery, the high-nickel-based lithium ion battery can simultaneously give consideration to energy density, cycle performance, storage performance and multiplying power performance.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium ion battery and a battery pack.
Background
At present, the lithium ion battery has the advantages of high capacity density, long cycle life, high charging speed and the like, and is widely applied to the fields of electronic products, electric vehicles, energy storage and the like. The NCM ternary positive electrode material is widely applied to a power battery of an electric automobile due to higher energy density, but with further improvement of the demand of the market for the endurance mileage of the electric automobile, the power battery is further required to have higher energy density, and the conventional NCM positive electrode material is insufficient to meet the demand.
Currently, there are two main approaches to increasing the energy density of a ternary battery:
the method has the advantages that the voltage of the battery is improved, but the higher voltage can cause oxidative decomposition of electrolyte, so that great difficulty is faced in further improving the voltage of the battery cell;
the proportion of Ni (nickel) content in the ternary material is improved, the energy density of the ternary battery can be further improved, but the higher the Ni content in the ternary material is, the easier the electrolyte is to be oxidized and decomposed, and the capacity of the battery core is rapidly attenuated.
In view of the foregoing, it is necessary to provide a solution to the above-mentioned problems.
Disclosure of Invention
One of the objects of the present invention is: a lithium ion battery is provided to solve the problem that the current nickel-based positive electrode battery cannot simultaneously give consideration to energy density, cycle performance and storage performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a lithium ion battery, comprising:
an electrolyte;
the battery cell comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate at intervals; the positive plate comprises a positive electrode active material layer, wherein a positive electrode active material in the positive electrode active material layer is a lithium nickel-based active material;
a housing for containing the electrolyte and the cell;
after the lithium ion battery is charged and discharged, a solid electrolyte interface film is formed on the surface of the positive electrode active material layer, at least the solid electrolyte interface film comprises sulfur element and boron element, and the weight ratio of the sum of the sulfur element and the boron element to the sum of the weights of the positive electrode active material layer and the solid electrolyte interface film is k, wherein the unit is wt%; taking the conductivity of the electrolyte as d, and the unit is mS/cm; the positive electrode active material layer has a compacted density ρ in g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The weight percentage of nickel element in the lithium nickel-based active material is r, and r is 20 to 60 weight percent; the following relationship is satisfied: and (100. D. K. Rho/r) is less than or equal to 0.3 and less than or equal to 45.
Preferably, 0.5.ltoreq.100.d.k.ρ/r.ltoreq.25.
Preferably, k is 0.01wt% to 0.2wt%.
Preferably, the electrolyte comprises a solvent, a lithium salt, and an additive comprising a sulfur-containing compound and a boron-containing compound; at least a part of the sulfur element in the sulfur-containing compound and at least a part of the boron element in the boron-containing compound migrate to the positive electrode active material layer to form a solid electrolyte interface film on the surface thereof.
Preferably, the mass percentage of the sulfur-containing compound in the electrolyte is 0.01-3.0 wt%; the mass percentage of the boron-containing compound in the electrolyte is 0.01-3.0wt%.
Preferably, the sulfur-containing compound is at least one of 1, 3-propane sultone, vinyl sulfate, methyl methylene disulfonate, 1-propylene-1, 3-sultone, 4-methyl ethylene sulfate, 4-ethyl ethylene sulfate, 4-propyl ethylene sulfate, propylene sulfate, 1, 4-butane sultone, ethylene sulfite, dimethyl sulfite and diethyl sulfite; the boron-containing compound is at least one of lithium dioxalate borate, lithium difluorooxalate borate and lithium tetrafluoroborate.
Preferably, the electrolyte has a conductivity d, measured at 25 ℃, of between 5 and 12mS/cm.
Preferably, the lithium nickel-based active material is Li 1+x Mn a Ni b M 1-a-b O 2-y A y And/or Li 1+z Ni c N 2-c O 4-d B d Wherein, -0.1 is less than or equal to x is less than or equal to 0.2, and 0 is less than or equal to a<1，0<b<1，0<a+b<1，0≤y<0.2, M is one or more of Co, fe, cr, ti, zn, V, al, zr and Ce, A is one or more of S, N, F, cl, br and I; -0.1.ltoreq.z.ltoreq.0.2, 0<c≤2，0≤d<1, n comprises one or more of Mn, fe, cr, ti, zn, V, al, mg, zr and Ce, and B comprises one or more of S, N, F, cl, br and I.
Preferably, the positive electrode active material layer has a compacted density ρ of 3.0 to 3.7g/cm 3 。
Preferably, the positive electrode active material layer has a single-sided surface density of 130 to 300g/m 2 。
Preferably, the negative electrode active material layer has a single-sided surface density of 50 to 150g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode active material layer has a compacted density of 1.3-1.8 g/cm 3 。
Another object of the present invention is to provide a battery pack comprising the lithium ion battery described in any one of the above.
Compared with the prior art, the invention has the beneficial effects that: the high-nickel lithium ion battery provided by the invention controls the weight percentage r of nickel element, synchronously limits the weight percentage k of sulfur element and boron element in the positive electrode active material layer, the conductivity d of electrolyte and the compaction density rho of the positive electrode active material layer, and 4 battery cores have higher energy density under the condition that the d.k.rho/r is less than or equal to 0.3 and less than or equal to 45, and the problems of the battery circulation performance and the storage performance are not influenced due to excessive nickel content, and meanwhile, the energy density, the circulation performance and the storage performance are simultaneously considered.
Detailed Description
1. Lithium ion battery
A first aspect of the present invention is directed to a lithium ion battery comprising an electrolyte, a cell, and a housing for containing the electrolyte and the cell.
The battery cell comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate at intervals; the positive plate comprises a positive electrode active material layer, wherein a positive electrode active material in the positive electrode active material layer is a lithium nickel-based active material; after the lithium ion battery is charged and discharged, a solid electrolyte interface film is formed on the surface of the positive electrode active material layer, at least the solid electrolyte interface film comprises sulfur element and boron element, and the weight ratio of the sum of the weight of the sulfur element and the weight of the boron element in the sum of the weight of the positive electrode active material layer and the weight of the solid electrolyte interface film is k, wherein the unit is wt%; taking the conductivity of the electrolyte as d, and the unit is mS/cm; the positive electrode active material layer has a compacted density ρ in g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The weight percentage of nickel element in the lithium nickel-based active material is r, and r is 20 to 60 weight percent; the following relationship is satisfied: and (100. D. K. Rho/r) is less than or equal to 0.3 and less than or equal to 45.
The sulfur element and the boron element may be contained only in the solid electrolyte interface film, or may be contained in the solid electrolyte interface film and the positive electrode active material layer. Specifically, the sulfur element and/or the boron element may be contained in the positive electrode active material layer, or may be doped in the lithium nickel-based active material layer, or may be doped in the positive electrode active material layer in an amount smaller than the content in the solid electrolyte interface film.
The solid electrolyte interface film contains sulfur element and silicon element, and can effectively prevent the oxidative decomposition of electrolyte by controlling the solid electrolyte interface film within the range of the relational expression, and can effectively prevent the oxidative decomposition of electrolyte even under the condition of higher nickel content, thereby improving the cycle performance and the storage life of the battery cell. The higher the k content, the more stable the solid electrolyte interface film is demonstrated, which is also more resistant to oxidative decomposition of the electrolyte. The inventors found that, compared with other substances or elements contained in the solid electrolyte interface film, the matching of the above relational expression can better achieve both cycle performance and storage performance while ensuring battery energy density for a high nickel-based battery by controlling the weight ratio of elemental sulfur and elemental boron.
The solid electrolyte interface film is an SEI film, which is in a dynamic decomposition and synthesis process, but the total weight of sulfur element and boron element in the positive electrode active material layer and the solid electrolyte interface film is not changed basically, the value of k can be any value at the charging moment, and preferably, the value of k is 50% of the value under the electric quantity state. Specifically, the lithium ion battery can be charged to 50% of electric quantity, then the positive plate is disassembled, after the weight of the positive current collector is removed, the rest substances are dissolved by aqua regia, the concentration of S and Si is measured by adopting an inductively coupled plasma emission spectrometer ICP, and then the weight of S and Si in unit area is converted, so that the weight is converted into the duty ratio k.
The specific k test steps are as follows:
1) ICP test conditions for S and Si contents were set:
the test conditions for ICP were:
plasma flow rate: 15L/min;
auxiliary flow: 0.3L/min;
atomizer flow rate: 0.6L/min;
radio frequency power: 1300W;
sample flow rate: 1.5L/min;
number of repetitions: 1, a step of;
observation direction: radial direction;
2) Standard sample solutions of S or Si were prepared: directly purchasing solutions with the concentration of 1000ug/mL in national or industry standard; taking 10mL of standard solution to a 100mL volumetric flask, adding 2mL of 2% nitric acid, adding pure water to dilute to a scale, and shaking uniformly for later use; taking 5 volumetric flasks, and respectively preparing sample standard solutions with the concentration of 0ug/mL,0.25ug/mL,0.5ug/mL,1.0ug/mL and 2.5ug/mL by using the diluted standard solutions; after ICP test equipment is stable, establishing a standard working curve of the element S or Si according to the test condition of 1), wherein the correlation coefficient of the standard working curve is more than or equal to 0.9995, otherwise, re-manufacturing a standard solution until the standard coefficient of the curve meets the requirement;
3) Preparing a solution of a sample to be tested: taking the air-dried area as S 0 50% of SOC positive plate, weighing, and recording the residual weight as m after removing the weight of the positive current collector P Ensuring the weight to be 0.35-0.50g (accurate to 0.1 mg); dissolving in aqua regia, heating on electric plate for 10min, cooling, and fixing volume to 100ml (ensuring that solubility of S or Si element in sample to be tested is within standard curve; if solubility is not determined, testing if concentration exceeds standard, further diluting)
4) Analyzing a sample to be tested: testing the sample to be analyzed under the test condition of 1), and respectively calculating the S and Si element concentrations C in the 50% SOC positive plate by ICP equipment 1 、C 2 The method comprises the steps of carrying out a first treatment on the surface of the Then converted into the area S according to the formula 0 The weight of the pole pieces S and Si;
wherein, the conversion formula is:
s weight M in 50% SOC positive plate S ＝C 1 *m P * Dilution factor/1000000/2;
si weight M in 50% SOC positive plate Si ＝C 2 *m P * Dilution factor/1000000/2;
k＝(M S +M Si )/m P 。
the conductivity d of the electrolyte needs to satisfy the above-described relational expression as well. In general, the higher the conductivity of the electrolyte, the faster the ion transport rate of the electrolyte, and the faster the chemical reaction rate of the electrode, and thus the stronger the rate discharge capacity of the battery, i.e., the stronger the power performance. The larger the weight ratio of S, B multiplied by the conductivity, the more stable the electrolyte is, the faster the transmission of lithium ions, the stronger the cycling performance of the lithium ion battery, and the higher the capacity retention.
In the lithium ion battery of the present invention, the compacted density ρ of the positive electrode active material layer also needs to satisfy the above-described relational expression. In general, the higher the compacted density, the lower the porosity in the electrode, the less the area of contact of the electrolyte with the active material is, the less side reactions, the less the electrolyte is susceptible to oxidative decomposition, the more favorable the long-term circulation and storage. In addition, for the solid electrolyte interface film formed by the invention, proper compaction density interacts with the solid electrolyte interface film, on one hand, the solid electrolyte interface film can play a role in preventing the oxidative decomposition of electrolyte, and meanwhile, the compaction density can synchronously reduce the contact probability of the electrolyte and active substances, so that the cycle performance and the storage performance are improved; on the other hand, the transportation of lithium ions is not affected due to the too low compaction density, so that the electrochemical performance is reduced.
The inventor finds that the product of the compaction density rho and k and d and the nickel content r can not only effectively improve the energy density of the battery, but also consider the cycle performance and the storage performance of the battery under the condition that the product accords with the relation. Generally, the higher the content of nickel element, the higher the charge-discharge capacity of the unit active material, but the higher the chemical activity of nickel element, the more easily the electrolyte is decomposed, resulting in rapid decay of the cell capacity; the invention synchronously controls rho, k and d, and can effectively reduce the risk of oxidative decomposition of electrolyte, thereby taking into account the cycle performance and storage performance of the battery under the condition of ensuring the energy density of the battery.
Specifically, the above relation may be: 0.3 & lt (100.d.k.ρ/r) & lt 3 & lt 1 & gt (100.d.k.ρ/r) & lt 5 & lt 3 & lt (100.d.k.ρ/r) & lt 5 & lt (100.d.k.ρ/r) & lt 8 & lt (100.d.k.ρ/r) & lt 10 & lt (100.d.k.ρ/r) & lt 13 & lt (100.d.k.ρ/r) & lt 15 & lt 100.d.k.ρ/r) & lt 18 & lt (100.d.k.ρ/r) & lt 20 & lt 20 < 23, 23 < 100.d.k.ρ/r < 25, 25 < 100.d.k.ρ/r < 28, 28 < 30, 30 < 100.d.k.ρ/r < 33, 33 < 35, 35 < 100.d.k.ρ/r < 35, 38 < 40 or 40 < 100.d.k.ρ/r < 45. Preferably, when the relational expression satisfies 0.5.ltoreq.100.d.k.ρ/r.ltoreq.25, the lithium ion battery has better energy density, cycle performance and storage performance. More preferably, when the relational expression satisfies 5.ltoreq.100.d.k.ρ/r.ltoreq.23, the lithium ion battery has better energy density, cycle performance and storage performance.
The weight percentage r of nickel element in the lithium nickel-based active material can be 20 to 25 weight percent, 25 to 30 weight percent, 30 to 35 weight percent, 30 to 40 weight percent, 40 to 45 weight percent, 45 to 50 weight percent, 50 to 55 weight percent or 55 to 60 weight percent. Preferably, r is 30 to 50wt%. The above-mentioned contents have been higher nickel contents than the conventional nickel setting contents. In contrast, the higher the nickel content is, the higher the energy density of the lithium ion battery is, but based on the battery integrity, the energy density of the battery can be better ensured only by ensuring that r, k, d and ρ meet the above relational expression, so that the energy density is more approximate to the theoretical energy density, and the cycle performance and the storage performance are simultaneously considered.
In some embodiments, k is 0.01wt% to 0.2wt%. Specifically, k may be 0.01 to 0.02wt%, 0.02 to 0.03wt%, 0.03 to 0.04wt%, 0.04 to 0.05wt%, 0.05 to 0.06wt%, 0.06 to 0.07wt%, 0.07 to 0.08wt%, 0.08 to 0.09wt%, 0.09 to 0.10wt%, 0.10 to 0.11wt%, 0.11 to 0.12wt%, 0.12 to 0.13wt%, 0.13 to 0.14wt%, 0.14 to 0.15wt%, 0.15 to 0.16wt%, 0.16 to 0.17wt%, 0.17 to 0.18wt%, 0.18 to 0.19wt%, or 0.19 to 0.20wt%. Preferably, k is 0.1wt% to 0.2wt% in accordance with the above relational expression. The more stable the generated solid electrolyte interface film is, the more effectively the side reaction between the positive electrode active material and the electrolyte can be prevented, and the oxidative decomposition of the electrolyte can be prevented, so that the cycle life of the battery can be effectively prolonged, and the capacity retention rate can be maintained.
In some embodiments, the electrolyte includes a solvent, a lithium salt, and an additive including a sulfur-containing compound and a boron-containing compound; at least a part of the sulfur element in the sulfur-containing compound and at least a part of the boron element in the boron-containing compound migrate to the positive electrode active material layer to form a solid electrolyte interface film on the surface thereof. The sulfur-containing compound and the boron-containing compound in the electrolyte can participate in the formation of the solid electrolyte interface film, and the sulfur element and the boron element remain in the interface film, so that a foundation is provided for preventing the electrolyte from oxidative decomposition subsequently.
In some embodiments, the mass percent of sulfur-containing compounds in the electrolyte is 0.01 to 3.0wt%; the mass percentage of the boron-containing compound in the electrolyte is 0.01-3.0wt%. The content of the two components is controlled to enable k to be in the range, and the battery has better cycle performance and storage performance by matching the relational expression.
In some embodiments, the sulfur-containing compound is at least one of 1, 3-propane sultone, vinyl sulfate, methylene methylsulfonate, 1-propylene-1, 3-sultone, 4-ethylethylene sulfate, 4-propylethylene sulfate, propylene sulfate, 1, 4-butane sultone, ethylene sulfite, dimethyl sulfite, and diethyl sulfite; the boron-containing compound is at least one of lithium dioxalate borate, lithium difluorooxalate borate and lithium tetrafluoroborate. Compared with other conventional electrolyte additives, the sulfur element and the boron element can participate in the formation of the solid electrolyte interface film and are matched with rho, r and d, so that the battery has better energy density, cycle performance and storage performance on the premise of meeting the relational expression.
In some embodiments, the additive further comprises at least one of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), succinonitrile (SN), hexadinitrile (ADN), 1,3, 6-Hexanetrinitrile (HTCN), 1,2, 3-tris (2-cyanooxy) propane, ethylene glycol bis (propionitrile) ether (EGBE), fluoroether.
In some embodiments, the electrolyte has a conductivity d, measured at 25 ℃, of from 5 to 12mS/cm. Specifically, d may be 5 to 6mS/cm, 6 to 7mS/cm, 7 to 8mS/cm, 8 to 9mS/cm, 9 to 10mS/cm, 10 to 11mS/cm, or 11 to 12mS/cm. Preferably, d is 8 to 12mS/cm. More preferably, d is 10 mS/cm. The selection of the above relation and the selection of k, r and ρ should be matched under the preferable d, so that the lithium ion battery has better energy density, cycle performance and storage performance.
In some embodiments, the lithium nickel-based active material is Li 1+x Mn a Ni b M 1-a-b O 2-y A y And/or Li 1+z Ni c N 2- c O 4-d B d Wherein, -0.1 is less than or equal to x is less than or equal to 0.2, and 0 is less than or equal to a<1，0<b<1，0<a+b<1，0≤y<0.2, M is one or more of Co, fe, cr, ti, zn, V, al, zr and Ce, A is one or more of S, N, F, cl, br and I; -0.1.ltoreq.z.ltoreq.0.2, 0<c≤2，0≤d<1, n comprises one or more of Mn, fe, cr, ti, zn, V, al, mg, zr and Ce, and B comprises one or more of S, N, F, cl, br and I. Wherein a and B in the lithium nickel-based active material refer to doping elements, which may preferably be S-doped. It also participates in the formation of the solid electrolyte interface film, and can better prevent the oxidative decomposition of the electrolyte within the range defined by the above relational expression.
In some embodiments, the positive electrode active material layer has a compacted density ρ of 3.0 to 3.7g/cm 3 . Specifically, the positive electrode active material layer may have a compacted density of 3.0 to 3.1g/cm 3 、3.1～3.2g/cm 3 、 3.2～3.3g/cm 3 、3.3～3.4g/cm 3 、3.4～3.5g/cm 3 、3.5～3.6g/cm 3 Or 3.6-37 g/cm 3 . Under the condition of optimizing compaction density, the contact between electrolyte and positive electrode active substances can be effectively prevented in the high-nickel lithium ion battery by matching the regulation and control of the relational expression, the electrolyte is not easy to oxidize and decompose, and the cycle performance and the storage performance of the battery are more excellent.
In some embodiments, the positive electrode active material layer has a single-sided area density of 130 to 300g/m 2 . Specifically, the single-sided surface density can be 130-150 g/m 2 、150～200g/m 2 、200～250g/m 2 Or 250-300 g/m 2 . Preferably, the single-sided surface density is 180-250 g/m 2 . In general, the lower the single-sided areal density, the less current collector (i.e., metal foil, such as aluminum foil) is used for the cells under the same capacity conditions, and the higher the energy density of the cells.
In some embodiments, the negative electrodeThe active material layer has a single-sided surface density of 50-150 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode active material layer has a compacted density of 1.3-1.8 g/cm 3 . The negative electrode also requires matching areal and compacted densities at higher energy densities of the positive electrode to better maintain battery cycling performance.
In some embodiments, the active material layer coated on the negative electrode sheet, the active material may be one or more of graphite, soft carbon, hard carbon, carbon fiber, mesophase carbon microsphere, silicon-based material, tin-based material, lithium titanate, or other metals capable of forming an alloy with lithium, etc. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon oxygen compound, silicon carbon compound and silicon alloy; the tin-based material can be selected from one or more of elemental tin, tin oxide and tin alloy. While the negative current collector used for the negative electrode sheet is generally a structure or a part for collecting current, the negative current collector may be various materials suitable for use as a negative current collector of a lithium ion battery in the field, for example, the negative current collector may be a metal foil, etc., and more specifically may include a copper foil, etc.
In some embodiments, the solvent in the electrolyte may be one or more of ethylene carbonate, propylene carbonate, and diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and methyl butyrate.
In some embodiments, the lithium salt in the electrolyte may be one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethanesulfonyl) imide, and lithium bis (fluorosulfonyl) imide.
In some embodiments, the separator may be one or more of PE, PP, ceramic, boehmite, PVDF, PMMA (acryl).
The positive plate, the diaphragm and the negative plate are sequentially wound or laminated to prepare the battery cell, and the conventional preparation can be referred to, and the description is omitted here.
The preparation method of the lithium ion battery can be referred to the existing preparation method as well, and the difference is that the raw material components of the lithium ion battery are required to conform to the relational expression of the invention, so that the obtained high-nickel lithium ion battery has high energy density and good cycle performance and storage performance.
2. Battery pack
A second aspect of the present invention is directed to a battery pack comprising the above-described lithium ion battery.
In order to make the technical solution and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A lithium ion battery comprising an electrolyte, a cell, and a housing for containing the electrolyte and the cell; the battery cell comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate at intervals; the positive plate comprises a positive electrode active material layer, wherein the positive electrode active material in the positive electrode active material layer is a lithium nickel-based active material, specifically Li 1.1 Mn 0.2 Ni 0.6 Co 0.2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode active material of the negative electrode plate is graphite; the diaphragm is a PP film; and the electrolyte comprises a solvent, lithium salt and an additive, wherein the solvent is a mixture of Ethylene Carbonate (EC), propylene Carbonate (PC), methyl ethyl carbonate (DEC) and Propyl Propionate (PP) in a mass ratio of 1:1:1:2, and the lithium salt is lithium hexafluorophosphate (LiPF) with the weight of 13.5 percent based on the total weight of the electrolyte 6 ) The additives include 0.5wt% of 1, 3-propane sultone, 1.0wt% of lithium difluorooxalato borate and 2.0wt% of fluoroethylene carbonate (FEC) based on the total weight of the electrolyte, and the specific preparation method of lithium ions can be referred to the existing preparation method and is not repeated here. Wherein the single-sided surface density of the positive electrode active material layer is 200g/m 2 The single-sided surface density of the negative electrode active material layer was 120g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode active material layer had a compacted density of 1.5g/cm 3 。
After the lithium ion battery is charged and discharged, the surface shape of the positive electrode active material layerForming a solid electrolyte interface film, wherein at least the solid electrolyte interface film comprises sulfur element and silicon element, and the weight ratio of the sum of the weight of the sulfur element and the weight of the silicon element in the sum of the weight of the positive electrode active material layer and the weight of the solid electrolyte interface film is k, wherein the unit is wt%; taking the conductivity of the electrolyte as d, and the unit is mS/cm; the positive electrode active material layer has a compacted density ρ in g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The weight percentage of nickel element in the lithium nickel-based active material is r, and the unit is wt%; specifically, k is 0.10wt%, d is 5mS/cm, and ρ is 3.4g/cm 3 R is 30wt%, calculated as (100·d·k·ρ)/r= (100×5×0.10×3.4)/30% =5.67.
See example 1 the following examples 2-29 are set forth with the difference that the values of k, d, ρ, r are given in table 1 below.
Performance tests, including cycle performance tests and high temperature storage performance tests, were performed on the lithium ion batteries obtained in examples 1 to 29.
1) And (3) cyclic test: at 25 ℃, charging the lithium ion secondary battery to 4.2V at a constant current of 0.5C, standing for 30min, discharging to 2.8V at a constant current of 1C, and standing for 30min, wherein the discharge capacity is the initial discharge capacity in the process of a charge-discharge cycle, and the number of cycles of the battery is recorded when the discharge capacity is reduced to 80% of the initial capacity.
2) High temperature storage test: charging the lithium ion secondary battery to 4.2V at a constant current of 1C, keeping the cut-off current of 0.05C, standing for 30min, discharging to 2.8V at a constant current of 1C, recording the capacity as C0 (initial capacity), and standing for 30min; the cells were placed in a 60 ℃ hot box and stored for 90 days, and the remaining capacity C1 and the recovery capacity C2 were tested every 30 days. The test of the residual capacity C1 is that after standing at 25 ℃ for 2 hours, 1C is discharged to 2.8V at constant current, and the capacity is recorded as C1 (residual capacity); then standing for 30min, charging to 4.2V at constant current and constant voltage of 1C, stopping current at 0.05C, standing for 30min, discharging to 2.8V at constant current of 1C, and recording the capacity as C2, wherein the capacity is recovered; capacity recovery for 90 days=c2 (day 90)/C0.
The test results are also shown in Table 1 below.
TABLE 1
As can be seen from the comparison of the above embodiments 1 to 29, the high nickel lithium ion battery provided by the present invention can better ensure that the battery has high energy density and better cycle performance and storage performance on the premise that the d, k, ρ and r satisfy the above relation, and can greatly improve the endurance capacity of the battery when used as a power battery, and further widen the application range of the lithium ion battery.
Specifically, as can be seen from the comparison of examples 1 to 8, as the conductivity d increases, the value of (100·d·k·ρ)/r increases as a molecule, and the cycle performance and storage performance of the lithium ion battery also improve. It is also evident from comparison of examples 6 and 16 to 22 that the higher the compacted density of the positive electrode active material layer is, (100·d·k·ρ)/r value is, the higher the cycle performance and storage performance of the lithium ion battery are improved.
In addition, as can be seen from the comparison of examples 6, 9 to 15, as the contents of S and B increase, the larger the value of k is, the larger the obtained value of (100·d·k·ρ)/r is, the more stable the generated solid electrolyte interface film is, the more effective the blocking of the contact of the electrolyte with the positive electrode active material is, thereby greatly relieving the oxidative decomposition of the electrolyte; however, if the k value is too large, the (100·d·k·ρ)/r value is beyond the above-mentioned protection range, the cycle performance and storage performance of the battery are adversely affected, which may be because the transportation of lithium ions is hindered even after the interfacial film thickness is too thick, thereby degrading the cycle performance and storage performance of the battery. In addition, by combining the comparison of examples 23-29, it can be further seen that the strong connection exists between k and r, and k which is matched with 0.20% is more suitable when the nickel content is 30%, so that the high-temperature storage capacity recovery can reach more than 99% in example 13; whereas a 20% nickel content preferably matches 0.10% k; however, at 40% higher nickel levels, k, either set at 0.20% or raised to higher levels, fails to give a higher degree of release of theoretical energy density, which may be a result of overall system impact. Therefore, the synergistic effect of d, k, rho and r is also demonstrated, and for the high-nickel lithium ion battery, the synchronous regulation and control of the data of the four can lead the lithium ion battery to have better cycle performance and storage performance on the premise of higher energy density under the condition of meeting the above relational expression.
In conclusion, the high-nickel-base positive electrode battery provided by the invention can ensure that the battery also has better cycle performance and storage performance on the premise of higher nickel content, and solves the problem that the existing nickel-base positive electrode battery cannot simultaneously consider the energy density, the cycle performance and the storage performance.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. A lithium ion battery, comprising:
an electrolyte comprising a solvent, a lithium salt, and an additive comprising a sulfur-containing compound and a boron-containing compound;
the battery cell comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate at intervals; the positive plate comprises a positive electrode active material layer, wherein a positive electrode active material in the positive electrode active material layer is a lithium nickel-based active material;
after the lithium ion battery is charged and discharged, a solid electrolyte interface film is formed on the surface of the positive electrode active material layer, and the sulfur-containing compound and the boron-containing compound in the additive are partially or completely converted into a solid electrolyte interface, so that the solid electrolyte interface film contains sulfur element and boron element, wherein the weight ratio of the sum of the sulfur element and the boron element to the sum of the weights of the positive electrode active material layer and the solid electrolyte interface film is k, the unit is wt%, and k is 0.01-0.2 wt%; by electricityThe conductivity of the solution is d, the unit mS/cm,the conductivity d of the electrolyte was measured at 25 DEG CD is 5-12 mS/cm; the positive electrode active material layer has a compacted density ρ in g/cm 3 Rho is 3.0-3.7 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The weight percentage of nickel element in the lithium nickel-based active material is r, and r is 30-60 wt%; the following relationship is satisfied: and (100. D. K. Rho/r) is less than or equal to 0.3 and less than or equal to 45.
2. The lithium ion battery of claim 1, wherein 0.5 +.100.d.k.ρ/r +.25.
3. The lithium ion battery of claim 1, wherein r is 36 to 60wt%.
4. The lithium ion battery according to any one of claims 1 to 2, wherein the electrolyte comprises a solvent, a lithium salt, and an additive comprising a sulfur-containing compound and a boron-containing compound; at least a part of the sulfur element in the sulfur-containing compound and at least a part of the boron element in the boron-containing compound migrate to the positive electrode active material layer to form a solid electrolyte interface film on the surface thereof.
5. The lithium ion battery according to claim 3, wherein the mass percentage of the sulfur-containing compound in the electrolyte is 0.01-3.0 wt%; the mass percentage of the boron-containing compound in the electrolyte is 0.01-3.0wt%.
6. The lithium ion battery of claim 4, wherein the sulfur-containing compound is at least one of 1, 3-propane sultone, vinyl sulfate, methylene methylsulfonate, 1-propylene-1, 3-sultone, 4-ethylethylene sulfate, 4-propylethylene sulfate, propylene sulfate, 1, 4-butane sultone, ethylene sulfite, dimethyl sulfite, and diethyl sulfite; the boron-containing compound is at least one of lithium dioxalate borate, lithium difluorooxalate borate and lithium tetrafluoroborate.
7. The lithium ion battery of claim 1, wherein the lithium nickel-based active material is Li 1+ x Mn a Ni b M 1-a-b O 2-y A y And/or Li 1+z Ni c N 2-c O 4-d B d Wherein, -0.1 is less than or equal to x is less than or equal to 0.2, and 0 is less than or equal to a<1，0<b<1，0<a+b<1，0≤y<0.2, M is one or more of Co, fe, cr, ti, zn, V, al, zr and Ce, A is one or more of S, N, F, cl, br and I; -0.1.ltoreq.z.ltoreq.0.2, 0<c≤2，0≤d<1, n comprises one or more of Mn, fe, cr, ti, zn, V, al, mg, zr and Ce, and B comprises one or more of S, N, F, cl, br and I.
8. The lithium ion battery according to claim 1, wherein the single-sided surface density of the positive electrode active material layer is 130 to 300g/m 2 。
9. The lithium ion battery according to claim 1, wherein the negative electrode active material layer has a single-sided area density of 50 to 150g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The negative electrode active material layer has a compacted density of 1.3-1.8 g/cm 3 。
10. A battery comprising a lithium-ion battery according to any one of claims 1 to 9.
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