CN109817955B - High-nickel positive electrode material for nonaqueous electrolyte secondary battery and preparation method thereof - Google Patents
High-nickel positive electrode material for nonaqueous electrolyte secondary battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high nickel anode material for a non-aqueous electrolyte secondary battery and a preparation method thereof, wherein the high nickel anode material has a general formula of LiwNi1‑x‑yCoxMnyMzO2It is shown that the average particle diameter D50 is 8 to 15 μm, the average particle diameter is composed of a small particle diameter D50 of 2 to 5 μm and a large particle diameter D50 of 8 to 18 μm, and the Co content (metal molar ratio; SC) of the small particle diameter is higher than that of the large particle diameter (metal molar ratio; LC), and the Co concentration ratio (SC/LC) is preferably in the range of 1.2 to 2. The high-nickel anode material stabilizes the material structure by doping and coating elements, and stabilizes the material crystal structure and improves the cycle performance of the material by improving the cobalt content in small particle size, and finally, the small particle size and the large particle size are mixed according to different proportions, so that the tap density of the anode material and the compaction density of a pole piece are improved.
Description
Technical Field
The present invention relates to a positive electrode material for a nonaqueous electrolyte secondary battery, and particularly to a high nickel positive electrode material composed of a high nickel composite oxide.
Technical Field
With the high-speed development of new energy vehicles, the demand for power batteries is continuously increased, in recent years, the new energy vehicles have higher and higher requirements for endurance mileage, and have higher challenges for the energy density, the cycle performance and the safety performance of lithium ion batteries. The high nickel-based positive electrode material has high capacity and low cost, so that the high nickel-based positive electrode material is a focus of attention of the positive electrode material and has a very wide market in the field of power batteries.
The high nickel positive electrode material has high nickel content and lithium ion radius
Radius of divalent nickel
The material is relatively close to the original material, so that lithium-nickel mixed arrangement is easily generated, the structural stability of the material is influenced, and the electrochemical performance of the material is further influenced; the particle size distribution of the high nickel-based positive electrode material in the current market is mostly normal distribution, the tap density of the particle size distribution material is low, the compaction density of the prepared pole piece is low, secondary particles are easy to break when the pole piece is rolled, the contact between the material and a conductive agent and a binding agent is poor, and meanwhile, the area of the interface between the material and an electrolyte is increased by breaking the particles, so that the electrochemical performance of the material is influenced; the mixed particle size distribution of the large particle size and the small particle size is a non-normal distribution with two peaks, and the small particle size particles can be filled in gaps among large particles, so that the tap density of the material and the compaction density of a pole piece can be effectively improved, but the specific surface area of the small particle size material is large, so that the material and electrolyte generate more side reactions, and the circulation stability of the material is poor. The application number 201710706178.1 stabilizes the crystal structure of the material by element doping, reduces residual alkali by water washing, and improves the electrochemical stability and safety by coating, but the tap density of the sample prepared by the method is relatively low; the application No. 201510545968.7 prepares materials with different particle sizes through precursors with different particle sizes, and the materials with different particle sizes are mixed to improve the material density, but the reaction of small particle sizes and electrolyte is not considered. Wood materialThe good cycle performance and the high tap density of the material cannot be obtained at the same time, so a novel high-nickel cathode material needs to be developed to solve the problems.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-nickel positive electrode material for a non-aqueous electrolyte secondary battery, which has high charge and discharge capacity and simultaneously has two characteristics of excellent cycle performance and higher tap density, and a preparation method thereof. The high-nickel anode material stabilizes the material structure by doping and coating elements, and stabilizes the material crystal structure and improves the cycle performance of the material by improving the cobalt content in small particle size, and finally, the small particle size and the large particle size are mixed according to different proportions, so that the tap density of the anode material and the compaction density of a pole piece are improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a high-Ni positive electrode material for non-aqueous electrolyte secondary battery is prepared from LiwNi1-x-yCoxMnyMzO2Wherein M is at least one element selected from Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg and Sr, W is more than or equal to 0.98 and less than or equal to 1.15, x is more than or equal to 0 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, and z is more than or equal to 0 and less than or equal to 0.02; the average particle diameter D50 of the high-nickel cathode material is 8-15 μm, and is composed of a small particle diameter D50 of 2-5 μm and a large particle diameter D50 of 8-18 μm, the mixing proportion of the small particle diameters is 10-90% in terms of mass ratio, and the cobalt content of the small particle diameters is higher than that of the large particle diameters.
The high-nickel cathode material is composed of large and small particle sizes, wherein the content (metal molar ratio; SC) of small-particle size Co is higher than that (metal molar ratio; LC) of large-particle size Co, the concentration ratio (SC/LC) of Co is preferably in the range of 1.2-2, particularly preferably 1.3-1.7, the too high concentration of Co influences the exertion of material capacity, and the too low Co element cannot play a role.
The key preparation technology of the high-nickel cathode material for the non-aqueous electrolyte secondary battery is characterized in that nickel-cobalt-manganese hydroxide/oxide with D50 of 2-5 mu m and cobalt content of 8-18 mu m different is adopted, lithium compounds and additives are respectively added for roasting, and then the mixture is mixed according to a certain proportion, so that the cobalt content (metal molar ratio: SC) with small particle size is higher than the cobalt content (metal molar ratio: LC) with large particle size, and the high-nickel cathode material with D50 of 8-15 mu m and composed of mixed particles is obtained.
In the method for manufacturing the high-nickel positive electrode material for the non-aqueous electrolyte secondary battery, the lithium compound is battery grade lithium carbonate or lithium hydroxide monohydrate, the average particle size D50 of the lithium compound is 5-8 μm, and the addition amount Li/(Ni + Co + Mn) of the lithium salt is 1.03-1.15 (in terms of molar ratio); the additive is selected from one of compounds containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr, and the particle size of the additive is between 10 and 100 nm; in the step of mixing the lithium compound and the additive with the nickel-cobalt-manganese hydroxide/oxide with different particle sizes, the nickel-cobalt-manganese hydroxide can be firstly oxidized and roasted to form the nickel-cobalt-manganese oxide, then the lithium compound is mixed, or the lithium compound and the additive can be directly mixed and then roasted, wherein the roasting temperature is 730 ℃ and 900 ℃, and the roasting time is 8-20 hours; the roasted material can be washed by water to reduce residual alkali, then is mixed with an additive to be roasted, and then is mixed according to a certain proportion after roasting to obtain a high-nickel anode material with D50 being 8-15 mu m, wherein the D50 is composed of mixed particles; if the material is washed by water, then mixed with an additive and then sintered, wherein the additive is selected from one of compounds containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr, the particle size of the additive is between 10 and 100nm, the sintering temperature is 400-700 ℃, and the sintering time is 3 to 10 hours.
In the method for manufacturing the high-nickel cathode material for the non-aqueous electrolyte secondary battery, the additive contains Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg, Sr and other elements, and the particle size of the additive is 10-100 nm. The additive has too large particle size, and the additive cannot be uniformly distributed in the material, so that elements in the additive are not uniformly distributed, and the due effect of the additive cannot be achieved.
The invention has the beneficial effects that: 1. the element doping can reduce the mixed arrangement of lithium and nickel, stabilize the crystal structure, reduce the side reaction between the material and the electrolyte by coating, improve the cycle performance, and improve the structural stability and the electrochemical performance of the material by the element doping and coating; the large and small particle sizes are mixed, and the small particle size particles can be filled in gaps among the large particle size particles, so that the space can be effectively utilized, and the tap density of the material and the compaction density of the pole piece can be improved; the cobalt element in the ternary material can stabilize the layered structure of the material and improve the cycle performance and the rate capability, and the problem of poor cycle stability caused by the reaction between the cobalt element in the small particle size and the electrolyte due to the large specific surface area of the small particle size is solved by improving the content of the cobalt element in the small particle size, so that the cycle performance of the small particle size material is improved, and the cycle performance after the large particle size and the small particle size are mixed is improved. The material has high tap density, is made into a pole piece and assembled into a battery, has high compaction density of the pole piece and good cycle performance of the battery, and thus realizes the coexistence of high tap density, high compaction density and good cycle performance. 2. The high-nickel positive electrode material for a non-aqueous electrolyte secondary battery has high charge-discharge characteristics and high tap density, and a lithium ion secondary battery assembled when the material is used as a positive electrode has high compaction density of a positive electrode sheet and good cycle performance of the battery. A lithium ion secondary battery using the positive electrode material of the present invention as a positive electrode material is suitable for a power supply mounted on a vehicle such as a hybrid vehicle or an electric vehicle, and is also suitable for use in the field of energy storage batteries and the like. 3. The high-nickel cathode material for the non-aqueous electrolyte secondary battery has high capacity and high tap density, can be suitably applied to large-sized secondary batteries for automobile carrying requiring good cycle performance and high compaction density, and has great industrial application value.
Drawings
FIG. 1 is a scanning electron micrograph of a high nickel positive electrode material obtained in example 1;
FIG. 2 is an XRD characterization of the high nickel positive electrode material obtained in example 1;
fig. 3 is a cycle chart of the high nickel cathode material obtained in example 1 under 0.5C condition.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The method for preparing the high nickel positive electrode material for the nonaqueous electrolyte secondary battery of the present embodiment is as follows:
(1) taking Ni with D50 of 12 mu m0.80Co0.10Mn0.10(OH)2Preparing a precursor, wherein a lithium source adopts lithium hydroxide monohydrate, the lithium source is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.03, an additive is 20nm nano magnesium oxide, the addition of magnesium element accounts for 0.005mol, the mixture is uniformly mixed by a ball mill, then the mixture is roasted for 12 hours at 780 ℃ in an oxygen air atmosphere, a roasted product is crushed and filtered by a 200-mesh screen, the dried product is washed by pure water, a certain amount of sample is taken, the additive is nano boron oxide, the addition of boron element accounts for 0.005mol, the mixture is uniformly mixed, then the mixture is roasted for 5 hours at 450 ℃ in an oxygen atmosphere, and finally the mixture is sieved, so as to obtain 12 mu m Li1.03Ni0.80Co0.10Mn0.10Mg0.005B0.005O2A material;
(2) taking Ni with D50 of 3 mu m0.80Co0.15Mn0.05(OH)2Preparing a precursor, wherein a lithium source adopts lithium hydroxide monohydrate, the lithium source is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.03, an additive is 20nm nano magnesium oxide, the addition of magnesium element accounts for 0.005mol, the mixture is uniformly mixed by a ball mill, then the mixture is roasted for 12 hours at 770 ℃ in an oxygen air atmosphere, the roasted product is crushed and filtered by a 200-mesh screen, the dried product is washed by pure water, a certain amount of sample is taken, the additive is nano boron oxide, the addition of boron element accounts for 0.005mol, the mixture is uniformly mixed, then the mixture is roasted for 5 hours at 450 ℃ in an oxygen atmosphere, and finally the mixture is sieved, so that 3 mu m Li is obtained1.03Ni0.80Co0.15Mn0.05Mg0.005B0.005O2A material;
(3) li to be prepared1.03Ni0.80Co0.10Mn0.10Mg0.005B0.005O2And Li1.03Ni0.80Co0.15Mn0.05Mg0.00 5B0.005O2The high-nickel cathode material is weighed according to the weight ratio of 2:8, and is uniformly mixed in a mixing tank to obtain the high-nickel cathode material with the overall particle size of 10 microns, wherein the cobalt concentration ratio (SC/LC) of small particle size to large particle size is 1.5.
The scanning electron micrograph of the high nickel cathode material of this example is shown in fig. 1. FIG. 2 shows the cycle performance of the obtained high-nickel cathode material at 0.5C/0.5C. Under the condition of 0.2C, the obtained material has the specific discharge capacity of 193mAh/g and higher specific discharge capacity, and after 100 cycles, the cycle retention rate is 92%, so that the material has better cycle performance. The tap density of the material was 2.72g/cm3The compacted density of the pole piece is 3.68g/cm3。
Example 2
The method for preparing the high nickel positive electrode material for the nonaqueous electrolyte secondary battery of the present embodiment is as follows:
(1) taking Ni with D50 of 13 mu m0.83Co0.08Mn0.09(OH)2Preparing a precursor, wherein a lithium source adopts lithium hydroxide monohydrate, the lithium source is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.04, an additive is 20nm of nano tungsten oxide, the addition of tungsten element accounts for 0.008mol, the mixture is uniformly mixed by a ball mill, then the mixture is roasted for 12 hours at 770 ℃ in an oxygen air atmosphere, the roasted product is crushed and filtered by a 200-mesh screen, the dried product is washed by pure water, a certain amount of sample is taken, the additive is nano tungsten oxide, the addition of tungsten element accounts for 0.005mol, the mixture is uniformly mixed, then the mixture is roasted for 5 hours at 500 ℃ in an oxygen atmosphere, and then the mixture is sieved, so that 13 mu m Li is obtained1.04Ni0.83Co0.08Mn0.09W0.013O2A material;
(2) taking Ni with D50 of 4 mu m0.83Co0.12Mn0.05(OH)2Preparing a precursor, wherein a lithium source adopts lithium hydroxide monohydrate, the lithium source is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.05, an additive is 20nm of nano tungsten oxide, the addition of tungsten element accounts for 0.008mol, the mixture is uniformly mixed by a ball mill, then the mixture is roasted for 12 hours at the temperature of 790 ℃ in an oxygen air atmosphere, a roasted product is crushed and passes through a 200-mesh screen, the pure water is used for washing and drying, a certain amount of sample is taken, and the additive is nanoTungsten oxide, the adding amount of the tungsten element accounts for 0.005mol, the tungsten element is evenly mixed and roasted for 5 hours at 500 ℃ in the oxygen atmosphere, and then the mixture is sieved to obtain Li with the particle size of 3 mu m1.05Ni0.83Co0.12Mn0.05W0.013O2A material;
(3) li prepared as described above1.04Ni0.83Co0.08Mn0.09W0.013O2And Li1.05Ni0.83Co0.12Mn0.05W0.013O2The high-nickel cathode material is weighed according to the weight ratio of 6:4, and is uniformly mixed in a mixing tank to obtain the high-nickel cathode material with the overall particle size of 10 microns, wherein the cobalt concentration ratio (SC/LC) of small particle size to large particle size is 1.5.
Under the condition of 0.2C, the discharge specific capacity of the obtained high-nickel anode material is 200mAh/g, the high-nickel anode material has high discharge specific capacity, and after 100 cycles, the cycle retention rate is 90%, and the high-nickel anode material has good cycle performance. The tap density of the material is 2.70g/cm3The compacted density of the pole piece is 3.70g/cm3。
Example 3
The method for preparing the high nickel positive electrode material for the nonaqueous electrolyte secondary battery of the present embodiment is as follows:
(1) taking Ni with D50 of 14 mu m0.65Co0.15Mn0.20(OH)2Preparing a precursor and a lithium source by adopting lithium carbonate in a molar ratio of Li/(Ni + Co + Mn) to 1.05, uniformly mixing an additive of 20nm nano-zirconia and a Zr element addition ratio of 0.01mol by using a ball mill, roasting for 12 hours at 860 ℃ in an oxygen air atmosphere, crushing a roasted product and sieving by using a 200-mesh sieve to obtain 15 mu m Li1.05Ni0.65Co0.15Mn0.20Zr0.01O2A material;
(2) taking Ni with D50 of 4 mu m0.65Co0.20Mn0.15(OH)2Preparing a precursor and a lithium source by adopting lithium carbonate in a molar ratio of Li/(Ni + Co + Mn) to 1.05, uniformly mixing an additive of 20nm nano-zirconia and Zr element in a ratio of 0.01mol by using a ball mill, and roasting for 12 hours at 840 ℃ in an oxygen air atmosphereIn this case, the calcined product was pulverized and sieved with a 200-mesh sieve to obtain 5 μm Li1.05Ni0.65Co0.20Mn0.15Zr0.01O2A material;
(3) mixing Li1.05Ni0.65Co0.15Mn0.20Zr0.01O2And Li1.05Ni0.65Co0.20Mn0.15Zr0.01O2The high nickel positive electrode material with the overall particle size of 12 microns is obtained after weighing according to the weight ratio of 7:3 and uniformly mixing in a mixing tank, wherein the cobalt concentration ratio (SC/LC) of the small particle size to the large particle size is 1.33.
Under the condition of 0.2C, the obtained high-nickel anode material has the specific discharge capacity of 182mAh/g and higher specific discharge capacity, the cycle retention rate is 94% after 100 cycles of cycle, the high-nickel anode material has better cycle performance, and the tap density of the material is 2.76g/cm3The compacted density of the pole piece is 3.72g/cm3。
Example 4
The method for preparing the high nickel positive electrode material for the nonaqueous electrolyte secondary battery of the present embodiment is as follows:
(1) taking Ni with D50 of 15 mu m0.82Co0.10Mn0.08(OH)2Preparing a precursor, wherein a lithium source adopts lithium hydroxide monohydrate, the lithium source is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.03, an additive is 20nm nano magnesium oxide, the addition of magnesium element accounts for 0.001mol, the mixture is uniformly mixed by a ball mill, then the mixture is roasted for 12 hours at 780 ℃ in an oxygen air atmosphere, the roasted product is crushed and filtered by a 200-mesh screen, the dried product is washed by pure water and then dried, a certain amount of sample is taken, the additive is nano boron oxide, the addition of boron element accounts for 0.01mol, the mixture is uniformly mixed and then roasted for 5 hours at 450 ℃ in an oxygen atmosphere, and finally the mixture is sieved, so that 12 mu m Li is obtained1.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2A material;
(2) taking Ni with D50 of 4 mu m0.80Co0.15Mn0.05(OH)2The precursor and the lithium source adopt lithium hydroxide monohydrate and are prepared in a mode that the molar ratio of Li/(Ni + Co + Mn) is 1.03The additive is 20nm nanometer strontium oxide, the adding amount of strontium element is 0.01mol, after being mixed evenly by a ball mill, the mixture is roasted for 12 hours under the oxygen air atmosphere at the temperature of 790 ℃, the roasted product is crushed and screened by a 200-mesh screen, a certain amount of sample is taken, the additive is nanometer boron oxide, the adding amount of boron element is 0.01mol, after being mixed evenly, the mixture is roasted for 5 hours at the temperature of 450 ℃, and then the mixture is screened, so that 4 mu m monocrystal Li is obtained1.03Ni0.80Co0.15Mn0.05Sr0.01B0.01O2A material;
(3) the two samples Li1.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2And Li1.03Ni0.80Co0.15Mn0.05Sr0.01B0.01O2The high nickel positive electrode material was weighed in a weight ratio of 2:8 and uniformly mixed in a mixing tank to obtain a high nickel positive electrode material having an overall particle size of 13.5 μm, wherein the cobalt concentration ratio (SC/LC) of small particle size to large particle size was 1.5.
Under the condition of 0.2C, the discharge specific capacity of the obtained high-nickel anode material is 193mAh/g, the high-nickel anode material has high discharge specific capacity, after 50 cycles, the cycle retention rate is 96%, and the high-nickel anode material has good cycle performance. The tap density of the material is 2.84g/cm3The compacted density of the pole piece is 3.73g/cm3。
Example 5
Sample i in example 41.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2And Li1.03Ni0.80Co0.15Mn0.05Sr0.01B0.01O2The high nickel cathode material with the overall particle size of 11 microns is obtained after weighing according to the weight ratio of 5:5 and uniformly mixing in a mixing tank, wherein the cobalt concentration ratio (SC/LC) of the small particle size to the large particle size is 1.5.
Under the condition of 0.2C, the discharge specific capacity of the obtained high-nickel anode material is 195mAh/g, the high-nickel anode material has high discharge specific capacity, and after 70 cycles, the cycle retention rate is 94%, and the high-nickel anode material has good cycle performance. The tap density of the material is 2.83g/cm3The compacted density of the pole piece is 3.77g/cm3。
Example 6
Sample i in example 41.03Ni0.82Co0.10Mn0.08Mg0.001B0.01O2And Li1.03Ni0.80Co0.15Mn0.05Sr0.01B0.01O2The high-nickel cathode material is weighed according to the weight ratio of 8:2, and is uniformly mixed in a mixing tank to obtain the high-nickel cathode material with the overall particle size of 9 mu m, wherein the cobalt concentration ratio (SC/LC) of the small particle size to the large particle size is 1.5.
Under the condition of 0.2C, the discharge specific capacity of the obtained high-nickel anode material is 197mAh/g, the high-nickel anode material has high discharge specific capacity, and after 50 cycles, the cycle retention rate is 95%, and the high-nickel anode material has good cycle performance. The tap density of the material is 2.86g/cm3The compacted density of the pole piece is 3.75g/cm3。
Example 7
The method for preparing the high nickel positive electrode material for the nonaqueous electrolyte secondary battery of the present embodiment is as follows:
(1) taking Ni with D50 of 18 mu m0.88Co0.05Mn0.07(OH)2Preparing a precursor, wherein a lithium source adopts lithium hydroxide monohydrate, the lithium source is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.07, an additive is 20nm of nano tungsten oxide, the addition amount of tungsten element accounts for 0.005mol, the mixture is uniformly mixed by a ball mill, then the mixture is roasted for 12 hours at 770 ℃ in an oxygen-air atmosphere, a roasted product is crushed and filtered by a 200-mesh screen, the dried product is washed by pure water and then dried, a certain amount of sample is taken, the additive is nano titanium oxide, the addition amount of titanium element accounts for 0.01mol, the mixture is uniformly mixed, then the mixture is roasted for 5 hours at 600 ℃ in an oxygen atmosphere, and then the mixture is sieved, so that 18 mu m Li is obtained1.07Ni0.88Co0.05Mn0.07W0.005Ti0.01O2A material;
(2) taking Ni with D50 of 4 mu m0.85Co0.10Mn0.05(OH)2The precursor and the lithium source adopt lithium hydroxide monohydrate, the lithium hydroxide monohydrate is prepared in a mode that the molar ratio is Li/(Ni + Co + Mn) ═ 1.05, and the additive is20nm nanometer zirconia, the adding amount of zirconium element is 0.01mol, after being mixed evenly by a ball mill, the mixture is roasted for 12 hours under the oxygen air atmosphere at 750 ℃, the roasted product is crushed and screened by a 200-mesh screen, washed by pure water and dried, a certain amount of sample is taken, the additive is nanometer titania, the adding amount of titanium element is 0.005mol, after being mixed evenly, the mixture is roasted for 5 hours at 500 ℃ and screened, 4 mu m Li is obtained1.05Ni0.85Co0.10Mn0.05Zr0.01Ti0.005O2A material;
(3) mixing Li1.05Ni0.85Co0.10Mn0.05Zr0.01Ti0.005O2And Li1.07Ni0.88Co0.05Mn0.07W0.005Ti0.01O2The high nickel cathode material with the overall particle size of 14 microns is obtained after weighing according to the weight ratio of 3:7 and uniformly mixing in a mixing tank, wherein the cobalt concentration ratio (SC/LC) of the small particle size to the large particle size is 2.
Under the condition of 0.2C, the discharge specific capacity of the obtained high-nickel anode material is 208mAh/g, the high-nickel anode material has high discharge specific capacity, and after 50 cycles, the cycle retention rate is 93%, and the high-nickel anode material has good cycle performance. The tap density of the material is 2.89g/cm3The compacted density of the pole piece is 3.80g/cm3。
Comparative example 1
Taking Ni with D50 of 14 mu m0.82Co0.10Mn0.08(OH)2Preparing a precursor and a lithium source by adopting lithium hydroxide monohydrate in a mode of molar ratio Li/(Ni + Co + Mn) being 1.03, uniformly mixing by using a ball mill, roasting for 12 hours at 780 ℃ in an oxygen air atmosphere, crushing a roasted product, sieving by using a 200-mesh sieve, washing by using pure water, drying, taking a certain amount of sample, uniformly mixing, roasting for 5 hours at 450 ℃ in an oxygen atmosphere, and sieving to obtain 14 mu m Li1.03Ni0.82Co0.10Mn0.08B0.01O2A material having a tap density of 2.62g/cm3Of pole piecesThe compacted density is 3.60g/cm3。
Comparative example 2
Taking Ni with D50 of 12 mu m0.65Co0.15Mn0.20(OH)2Preparing a precursor and a lithium source by adopting lithium carbonate in a molar ratio of Li/(Ni + Co + Mn) to 1.05, uniformly mixing an additive of 20nm nano-zirconia and Zr element in a ratio of 0.01mol by using a ball mill, roasting for 12 hours at 860 ℃ in an oxygen air atmosphere, crushing a roasted product and sieving by using a 200-mesh sieve to obtain Li1.05Ni0.65Co0.15Mn0.20Zr0.01O2A material having a tap density of 2.58g/cm3The compacted density of the pole piece is 3.58g/cm3。
Comparative example 3
Taking Ni with D50 of 4 mu m0.80Co0.15Mn0.05(OH)2Preparing a precursor and a lithium source by adopting lithium hydroxide monohydrate in a mode of molar ratio Li/(Ni + Co + Mn) being 1.03, uniformly mixing by using a ball mill, roasting for 12 hours at 790 ℃ in an oxygen-air atmosphere, crushing a roasted product, sieving by using a 200-mesh sieve, washing, adding nano zirconium dioxide in an oxygen atmosphere, roasting for 5 hours at 450 ℃, and sieving to obtain 4 mu m Li1.03Ni0.80Co0.15Mn0.05Zr0.0 2O2A material having a tap density of 2.42g/cm3The compacted density of the pole piece is 3.25g/cm3。
The results of the above tests are shown in the following table.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A high-nickel positive electrode material for a nonaqueous electrolyte secondary battery, characterized in that: the positive electrode material has a general formula of LiwNi1-x-yCoxMnyMzO2Expressed in that M is at least one element selected from Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg and Sr, W is more than or equal to 0.98 and less than or equal to 1.15, x is more than or equal to 0 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, z is more than or equal to 0 and less than or equal to 0.02, the average particle size D50 is 8-15 mu M and consists of a small particle size with the D50 of 2-5 mu M and a large particle size with the D50 of 8-18 mu M, the mixing ratio of the small particle sizes is 10-90% by mass, and the cobalt content of the small particle size is higher than that of the large particle size by metal molar;
the metal molar ratio SC of the Co content with small particle size is higher than the metal molar ratio LC of the Co content with large particle size, and the Co concentration ratio SC/LC is in the range of 1.2-2.
2. The method for producing a high-nickel positive electrode material for a nonaqueous electrolyte secondary battery according to claim 1, characterized in that:
(1) respectively selecting nickel-cobalt-manganese hydroxide/oxide with different cobalt contents, wherein D50 is 2-5 mu m and D50 is 8-18 mu m;
(2) adding a lithium compound and an additive into the nickel-cobalt-manganese hydroxide/oxide, roasting, and mixing at a certain ratio to enable the cobalt content of the small particle size to be higher than that of the large particle size, thereby obtaining the high-nickel cathode material with the average particle size D50 of 8-15 mu m and composed of mixed particles.
3. The method for producing a high-nickel positive electrode material for a nonaqueous electrolyte secondary battery according to claim 2, characterized in that: the lithium compound in the step (2) is selected from battery grade lithium carbonate or battery grade lithium hydroxide monohydrate, the average particle size D50 of the lithium compound is 5-8 μm, and the addition amount of the lithium salt Li/(Ni + Co + Mn) is 1.03-1.15 in molar ratio; the additive is selected from one of compounds containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr, and the particle size of the additive is 10-100 nm.
4. The method for producing a high-nickel positive electrode material for a nonaqueous electrolyte secondary battery according to claim 2, characterized in that: in the step (2), the roasting temperature is 730-900 ℃, and the roasting time is 8-20 h.
5. The method for producing a high-nickel positive electrode material for a nonaqueous electrolyte secondary battery according to claim 2, characterized in that: and (3) washing the roasted material in the step (2) with water to reduce residual alkali, mixing with an additive, roasting, and mixing according to a certain proportion after roasting.
6. The method for producing a high-nickel positive electrode material for a nonaqueous electrolyte secondary battery according to claim 2, characterized in that: the additive is selected from one of compounds containing Zr, Mg, Ti, Ce, Mo, W, Nb, B, F, Ca, Mg or Sr, and the particle size of the additive is 10-100 nm.
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| CN110380034A (en) * | 2019-07-23 | 2019-10-25 | 合肥国轩高科动力能源有限公司 | A kind of positive electrode of lithium ion battery and full battery and preparation method containing it |
| KR20210031325A (en) | 2019-09-11 | 2021-03-19 | 주식회사 엘지화학 | Positive electrode material for secondary battery and lithium secondary battery comprising the same |
| KR20210070933A (en) * | 2019-12-05 | 2021-06-15 | 주식회사 엘지에너지솔루션 | Positive electrode active material for lithium secondary battery and preparing method of the same |
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| CN111058084B (en) * | 2019-12-25 | 2022-02-01 | 湖北融通高科先进材料有限公司 | Method for preparing nickel cobalt lithium manganate single crystal ternary material |
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| CN112194200A (en) * | 2020-08-27 | 2021-01-08 | 浙江美都海创锂电科技有限公司 | Preparation method of high-nickel cathode material with low residual alkali, high compaction and uniform coating layer |
| CN112201784B (en) * | 2020-09-28 | 2022-04-12 | 中创新航技术研究院(江苏)有限公司 | Positive electrode material, preparation method and application thereof |
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| CN114725344A (en) * | 2022-04-20 | 2022-07-08 | 天津巴莫科技有限责任公司 | High-nickel positive electrode material, preparation method thereof and lithium ion battery |
| CN115763759A (en) * | 2022-11-30 | 2023-03-07 | 巴斯夫杉杉电池材料(宁乡)有限公司 | Positive active material with matched large and small particles and preparation method thereof |
| CN116344791B (en) * | 2023-05-26 | 2023-08-08 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
| CN117080415B (en) * | 2023-10-13 | 2024-02-27 | 宁德时代新能源科技股份有限公司 | Positive electrode active material composition, positive electrode plate, battery and electric equipment |
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