CN113735193A - High-capacity lithium ion battery - Google Patents
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Abstract
The invention discloses a high-capacity lithium ion battery which comprises a positive electrode material, a negative electrode material and electrolyte. The chemical formula of the anode material is LiNi(1‑x)MexO and x are 10‑6～10‑1Me is a third metal other than Li and Ni. The material has the characteristics of high purity, high density, high lithium removal capacity and the like. The preparation method of the cathode material comprises the following steps: selecting nickel salt and additive, adopting chemical coprecipitation method, calcining, inducing environment, inducing chemical substance and their combination to induce crack structure to obtain precursor, mixing with Li2And mixing, sintering and crushing the O to obtain the cathode material. The crystal structure is changed to form cracks through the induction of the induction environment or the induction of chemical substances,and the unit cell volume is further enlarged, so that lithium ions can react with NiO more fully, the segregation is reduced, the purity and the density of the pre-lithium material are improved, the lithium removal capacity is improved, and the integral capacitance of the lithium ion battery is promoted to be improved.
Description
The invention is a divisional application of patent application with application number 202110009043.6, application date 2021, 1 month and 5 days, entitled pre-lithium material and preparation method thereof.
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a pre-lithium material, in particular to a high-purity pre-lithium material and a preparation method thereof.
Background
In order to improve the energy density of the lithium ion battery, a silicon negative electrode material with high specific capacity is gradually becoming the choice of battery enterprises and material suppliers, and becomes one of the most potential next-generation lithium ion battery negative electrode materials. However, the large volume expansion and low first coulombic efficiency of silicon anodes limit their practical applications. Because the coulombic efficiency of the cathode material is far higher than that of the cathode, the capacity of the cathode material cannot be fully exerted, and the waste of the cathode material and the reduction of the battery capacity are caused. This is mainly because the surface of the anode material forms a solid electrolyte film, i.e., an SEI film, during the first charge, which consumes lithium ions, while in the battery, lithium ions are almost entirely supplied from the cathode material. Therefore, the concept of "lithium replenishment" has been proposed to replenish lithium ions consumed by the SEI film formation during the first charge of the battery by "replenishing lithium" on the negative electrode, positive electrode or separator.
The positive pole lithium supplementing process is that during the homogenization of the positive pole, high lithium capacity material is added, and during the charging process, the surplus lithium element is extracted from the high lithium capacity positive pole material and is inserted into the negative pole to supplement the irreversible lithium capacity of the first charge and discharge.
Therefore, a lithium source is found from the outside of the positive electrode material, and lithium ions of the external lithium source are consumed in the formation of the SEI film, so that the waste of the lithium ions deintercalated from the positive electrode material can be ensured, and the full battery capacity can be improved finally. This process of providing an external source of lithium, referred to as a pre-lithium material, is pre-lithiation.
The research of the pre-lithium material is a research hotspot in the field of lithium batteries in recent years, and patent CN 107221650B mentions a lithium supplement additive and a preparation method thereof, which are completed by mixing a plurality of substances in a certain proportion and sintering in multiple steps, but the purity of active ingredients is low, partial products have small particles and high activity, so that the storage is difficult, passivation treatment is needed, and the process is complex. Patent CN 107819113a discloses a lithium supplement additive, its preparation method and application, wherein the lithium supplement additive is a core-shell structure, the core material is conductive carbon material, and the shell material is lithium oxide; the lithium oxide is deposited on the surface of the conductive carbon material, and the nano-layer shell is formed by the lithium oxide particles with the nano-size, so the preparation process is complex and has high difficulty.
In the prior patents and research, Li was synthesized2NiO2The raw material and the method mainly select Li2Solid-phase synthesis with O/LiOH and the corresponding nickel salts and addition of additives, but in the actual synthesis process it was found that Li can be synthesized despite the fact that Li is present2NiO2The sample has larger impurity components and lower content, and the main reason is that NiO is easy to agglomerate and segregate in the synthesis process and has poor reproducibility.
Therefore, the research on a pre-lithium material with high purity and good lithium supplementing performance becomes a research focus at present.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provide a pre-lithium material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to one aspect of the present invention, there is provided a pre-lithium material having the formula LiNi(1-x)MexO, wherein x is 10-6～10-1Me is a third metal other than Li and Ni.
According to an embodiment of the present invention, the third metal is one or two or more elements selected from Sr, Y, Nb, Ce, Ta, Mo, and W.
According to one embodiment of the invention, the pre-lithium material contains cracks, the width of which is 0.5nm to 1nm or 1nm to 100nm, and the length of which is 0.5nm to 1nm or 1nm to 500 nm.
According to one embodiment of the invention, the pre-lithium material has a median particle diameter D50 of 1 μm to 20 μm and a specific surface area of 0.1m2/g～100m2(ii)/g; preferably, the pre-lithium material has a median particle diameter D50 of 3 μm to 15 μm and a specific surface area of 5m2/g～50m2/g。
According to another aspect of the present invention, there is provided a method for preparing a pre-lithium material, comprising the main steps of:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, inducing the precursor 2 to induce a crack structure to prepare a precursor 3;
s4 mixing the precursor 3 with Li in equal molar ratio2And O, mixing, sintering in an inert atmosphere, and crushing to prepare the pre-lithium material.
According to an embodiment of the present invention, the nickel salt includes one or more of nickel sulfate, nickel nitrate, nickel chloride, and nickel bromide.
According to an embodiment of the invention, the additive comprises one or a mixture of two or more of compounds containing Sr, Y, Nb, Ce, Ta, Mo or W.
According to an embodiment of the present invention, the chemical formula of the precursor 2 is Ni(1-x)MexAnd O, wherein the total content of free water and crystal water in the precursor 2 is controlled within 0.001 percent in terms of mole percentage.
According to an embodiment of the present invention, the inert gas is selected from the group consisting of nitrogen, helium, neon, argon, and mixtures thereof.
According to an embodiment of the present invention, the inducing operation is a treatment performed by placing in an inducing environment, adding an inducing chemical, or placing in an inducing environment by adding an inducing chemical.
According to an embodiment of the present invention, the induction environment includes a low temperature environment, a high pressure environment, a high temperature quenching environment, and a combination thereof.
According to an embodiment of the present invention, the temperature of the low temperature environment is-100 ℃ to-250 ℃.
According to an embodiment of the present invention, the pressure of the high pressure environment is 10bar to 500 bar.
According to an embodiment of the invention, the high-temperature quenching environment is that the temperature is firstly heated to 300-800 ℃, and then the temperature is rapidly reduced to the room temperature in liquid nitrogen.
According to an embodiment of the invention, the inducing chemical comprises one or a mixture of two or more of the compounds of Sr, Y, Nb, Ce, Ta, Mo or W.
Compared with the prior art, the invention has the beneficial effects that:
1. the pre-lithium material has the characteristics of high purity, high density, high lithium removal capacity and the like;
2. in the method for preparing the pre-lithium material, the crystal structure is changed and the unit cell volume is further enlarged by the induction action of the induction environment or the induction chemical substances, so that lithium ions can react with NiO more fully, thereby reducing segregation, improving the purity and density of the pre-lithium material, further improving the lithium removal capacity and promoting the improvement of the integral capacity of the lithium ion battery.
Drawings
FIG. 1 is an SEM photograph of example 2;
fig. 2 is a first charge capacity map of example 2.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be construed as limiting the invention.
In one embodiment of the present invention, a pre-lithium material is provided having a chemical formula of LiNi(1-x)MexO, wherein x is 10-6～10-1For example x is 10-6、10-5、10-4、10-3、10-2、10-1(ii) a Me is a third metal other than Li and Ni,
in one embodiment of the present invention, the third metal includes one or more elements selected from Sr, Y, Nb, Ce, Ta, Mo, and W.
In one embodiment of the invention, the pre-lithium material contains cracks with a width of 0.5nm to 1nm or 1nm to 100nm, for example with a width of 0.5nm, 0.8nm, 1nm, 10nm, 100 nm; the crack length is 0.5nm to 1nm or 1nm to 500nm, for example, the crack length is 0.5nm, 0.8nm, 1nm, 10nm, 20nm, 200nm, 300nm, 400nm, or 500 nm.
In one embodiment of the present invention, the median particle size D50 of the pre-lithium material is 1 μm to 20 μm, for example, the median particle size D50 of the pre-lithium material is 1 μm, 5 μm, 10 μm, 16 μm, 20 μm; preferably, the median particle size D50 of the pre-lithium material is from 3 μm to 15 μm, for example, the median particle size D50 of the pre-lithium material is 3 μm, 6 μm, 9 μm, 12 μm, 15 μm
In one embodiment of the present invention, the specific surface area of the pre-lithium material is 0.1m2/g～100m2In g, e.g. a specific surface area of the pre-lithium material of 0.1m2/g、10m2/g、60m2/g、100m2(ii)/g; preferably, the pre-lithium material has a specific surface area of 5m2/g～50m2In g, e.g. the specific surface area of the pre-lithium material is 5m2/g、20m2/g、30m2/g、40m2/g、50m2/g。
The invention provides a preparation method of a pre-lithium material, which mainly comprises the following steps:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, inducing the precursor 2 to induce a crack structure to prepare a precursor 3;
s4 mixing the precursor 3 with Li in equal molar ratio2And O, mixing, sintering in an inert atmosphere, and crushing to prepare the pre-lithium material.
In one embodiment of the present invention, the nickel salt includes one or more of nickel sulfate, nickel nitrate, nickel chloride, and nickel bromide.
In one embodiment of the present invention, the additive comprises one or a mixture of two or more of compounds containing Sr, Y, Nb, Ce, Ta, Mo, W. Wherein the Sr compound comprises SrCO3SrO or SrSO4The compound of Y includes Y (NO)3)3、Y2(SO4)3、Y2O3、YBr3Or Y2(CO3)3The Nb compound includes LiNbO3、NbCl5Or NbN, Ce compounds including CeCl3、CeBr3Or Ce2O3Compounds of Ta include TaCl5Or TaBr5The compound of Mo includes MoO3、Mo(SO4)3Or Mo (NO)3)3The compound of W is Na2WF8。
In one embodiment of the present invention, the chemical formula of the precursor 2 is Ni(1-x)MexO, the total content of free water and crystal water in the precursor 2 is controlled to be within 0.001%, for example, 0.001%, 0.0008%, 0.0006%, 0.0004%, 0.0002% in terms of mole percent.
In one embodiment of the present invention, the inert gas includes nitrogen, helium, neon, argon and mixtures thereof.
In one embodiment of the present invention, the inducing operation is a treatment performed by placing in an inducing environment, adding an inducing chemical, or placing in an inducing environment and adding an inducing chemical.
In one embodiment of the present invention, the inducing environment includes a low temperature environment, a high pressure environment, a high temperature quenching environment, and a combination thereof.
In one embodiment of the present invention, the temperature of the low temperature environment is-100 ℃ to-250 ℃, for example-100 ℃, 150 ℃, 200 ℃ and 250 ℃.
In one embodiment of the invention, the high pressure environment has a pressure of 10bar to 500bar, for example 100bar, 200bar, 400bar, 500 bar.
In one embodiment of the present invention, the high temperature quenching environment is first heated to 300-800 deg.C, then heated to 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, and then rapidly cooled to room temperature in liquid nitrogen.
In one embodiment of the present invention, the inducing chemical includes one or a mixture of two or more of Sr, Y, Nb, Ce, Ta, Mo, or W compounds. Wherein the Sr compound comprises SrCO3SrO or SrSO4The compound of Y includes Y (NO)3)3、Y2(SO4)3、Y2O3、YBr3Or Y2(CO3)3The Nb compound includes LiNbO3、NbCl5Or NbN, Ce compounds including CeCl3、CeBr3Or Ce2O3Compounds of Ta include TaCl5Or TaBr5The compound of Mo includes MoO3、Mo(SO4)3Or Mo (NO)3)3The compound of W is Na2WF8。
The pre-lithium material and the preparation method thereof according to the present invention will be further described with reference to the following embodiments.
Example 1
Taking 10kg of analytically pure nickel sulfate and 0.01g of analytically pure cerium sulfate as raw materials, preparing into 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container for reaction, filtering, washing and drying precipitates to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Ce and x is 10-5(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO, where Me is Ce and x is 10-5(ii) a 0.005g of cerium sulfate as an induction chemical was added to the precursor 2Mixing uniformly, placing in liquid nitrogen-196 deg.C environment for 60min, inducing crystal structure mutagenesis under the cooperation of low temperature environment and inducing chemical substance, changing crystal grain size, and preparing precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in a nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to a median particle size D50 of 10 mu m, and preparing a pre-lithium material, wherein the pre-lithium material contains cracks, the width and length of small cracks are 0.5-1 nm, the width and length of large cracks are 1-50 nm and 10-400 nm respectively, the purity of the pre-lithium material is 94.5%, the pre-lithium material is taken as a lithium battery anode material, graphite is taken as a lithium battery cathode material, and ethyl carbonate solution of lithium hexafluorophosphate is taken as electrolyte to jointly prepare the lithium ion battery, and the 4.5V first charge capacity of the battery is 410.5 mAh/g.
Example 2
Taking 10kg of analytically pure nickel chloride and 0.1g of analytically pure niobium pentachloride as raw materials, preparing into 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container for reaction, filtering, washing and drying precipitates to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Nb and x is 10-3(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO, where Me is Nb and x is 10-3(ii) a Adding 0.02g of inducing chemical substance niobium pentachloride into the precursor 2, uniformly mixing, then placing in an isostatic pressing environment, pressing to 150bar, pressurizing for 30min, heating to 500 ℃ after decompression, heating for 60min, cooling to room temperature at a very high speed by liquid nitrogen, inducing crystal structure mutagenesis under the cooperation of the pressurizing environment and the inducing chemical substance, changing the grain size of the crystal structure, and preparing a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in nitrogen atmosphere at 800 deg.C under 40bar pressure for 80min, and coolingAnd (2) cooling to room temperature, crushing to a median diameter D50 of 10 μm, and preparing a pre-lithium material, wherein the pre-lithium material contains cracks, the width and the length of each small crack are 0.5-0.8 nm, the width and the length of each large crack are 1-90 nm and 5-300 nm respectively, the purity of the pre-lithium material is 97.6%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is used as an electrolyte to jointly prepare a lithium ion battery, and the 4.5V first charge capacity of the battery is 431.1 mAh/g.
Example 3
Taking 10kg of analytically pure nickel bromide and 0.005g of analytically pure tantalum bromide as raw materials, preparing into 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container for reaction, filtering, washing and drying precipitates to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Ta and x is 10-6(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO, where Me is Ta and x is 10-6(ii) a Adding 0.02g of inducing chemical tantalum bromide into the precursor 2, heating to 800 ℃, wherein the heating time is 60min, cooling to room temperature at a high speed by liquid nitrogen to induce martensite phase transformation, inducing crystal structure mutagenesis under the cooperation of a high-temperature quenching environment and the inducing chemical, and changing the grain size of the crystal structure to prepare a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to the median diameter D50 of 10 mu m, preparing a pre-lithium material, wherein the pre-lithium material contains cracks, the width and the length of small cracks are 0.5-0.7 nm, the width and the length of large cracks are 3-70 nm and 5-500 nm respectively, the purity of the pre-lithium material is 96.1%, and a lithium ion battery and an electric battery which are prepared by taking the pre-lithium material as a lithium battery anode material, graphite as a lithium battery cathode material and ethyl carbonate solution of lithium hexafluorophosphate as electrolyteThe 4.5V first charge capacity of the cell was 423.2 mAh/g.
Example 4
Mixing 10kg of analytically pure nickel sulfate, 0.01g of analytically pure yttrium sulfate and analytically pure strontium sulfate in equal ratio to prepare 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container to react, filtering, washing and drying the precipitate to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Y and Sr, and x is 10-5(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO, where Me is Ce and x is 10-5(ii) a Adding 0.005g of inducing chemical cerium sulfate into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, inducing the crystal structure under the cooperation of a low-temperature environment and the inducing chemical, and changing the grain size of the crystal structure to prepare a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in a nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to a median particle size D50 of 10 mu m, and preparing a pre-lithium material, wherein the pre-lithium material contains cracks, the width and length of small cracks are 0.5-1 nm, the width and length of large cracks are 8-90 nm and 4-450 nm respectively, the purity of the pre-lithium material is 95.1%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to jointly prepare the lithium ion battery, and the 4.5V primary charge capacity of the battery is 413.6 mAh/g.
Example 5
10kg of analytically pure nickel sulfate, 0.002g of analytically pure yttrium sulfate, analytically pure strontium sulfate, niobium pentachloride, cerium sulfate and tantalum bromide are mixed in equal ratio to serve as raw materials to prepare 1mol/L sulfate solution, 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water are added into a reaction container to reactFiltering, washing and drying the precipitate to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Sr, Y, Nb, Ce and Ta, and x is 10-5(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO, wherein Me is Sr, Y, Nb, Ce and Ta, and x is 10-5(ii) a Adding 0.01g of inducing chemical tantalum bromide into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, inducing crystal structure mutagenesis under the cooperation of a low-temperature environment and the inducing chemical, changing the grain size of the crystal structure, and preparing a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in a nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to the median diameter D50 of 10 mu m, and preparing a pre-lithium material, wherein the pre-lithium material contains cracks, the width and the length of each small crack are 0.5-0.9 nm, the width and the length of each large crack are 2-50 nm and 15-350 nm respectively, the purity of the pre-lithium material is 95.6%, the pre-lithium material is taken as a lithium battery anode material, graphite is taken as a lithium battery cathode material, and the lithium battery is prepared by taking ethyl carbonate solution of lithium hexafluorophosphate as electrolyte, and the 4.5V first charge capacity of the battery is 416.1 mAh/g.
Example 6
Mixing 10kg of analytically pure nickel sulfate, 0.001g of analytically pure yttrium sulfate, analytically pure strontium sulfate, niobium pentachloride, cerium sulfate and tantalum bromide in equal ratio to obtain raw materials, preparing a 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container to react, filtering, washing and drying precipitates to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Sr, Y, Nb, Ce and Ta, and x is 10-6(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO，Wherein Me is Sr, Y, Nb, Ce and Ta, and x is 10-6(ii) a Adding 0.015g of inducing chemical tantalum bromide into the precursor 2, uniformly mixing, placing in a liquid nitrogen-150 ℃ environment for 60min, inducing crystal structure mutagenesis under the cooperation of a low-temperature environment and the inducing chemical, changing the grain size of the crystal structure, and preparing a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in a nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to a median particle size D50 of 10 mu m, and preparing a pre-lithium material, wherein the pre-lithium material contains cracks, the width and length of small cracks are 0.6-1 nm, the width and length of large cracks are 20-80 nm and 30-450 nm respectively, the purity of the pre-lithium material is 94.7%, the pre-lithium material is used as a lithium battery anode material, graphite is used as a lithium battery cathode material, and ethyl carbonate solution of lithium hexafluorophosphate is used as electrolyte to jointly prepare the lithium ion battery, and the 4.5V primary charge capacity of the battery is 413.2 mAh/g.
Comparative example 1
Taking 10kg of analytically pure nickel sulfate as a raw material, preparing a 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container to react, filtering, washing and drying precipitates to prepare a precursor 1, which is recorded as Ni (OH)2(ii) a Sintering in a nitrogen atmosphere, wherein the pressure applied to sintering is 30bar, the sintering temperature is 750 ℃, and the sintering time is 60min, so as to prepare a precursor 2, and the precursor is recorded as NiO; adding 0.005g of inducing chemical cerium sulfate into the precursor 2, uniformly mixing, heating the mixture to 700 ℃, wherein the heating time is 60min, then rapidly cooling to room temperature through liquid nitrogen to induce martensite phase transformation, placing the mixture in a liquid nitrogen-196 ℃ environment for 60min, inducing crystal structure mutagenesis in a high-temperature quenching environment, a low-temperature environment and the inducing chemical substances under the cooperation of the high-temperature quenching environment, the low-temperature environment and the inducing chemical substances, and changing the grain size of the crystal structure to prepare a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in nitrogen atmosphere at 800 deg.C under 40bar for 80min, cooling to room temperature, and sintering at room temperatureCrushing to a median particle size D50 of 10 μm, preparing a sample of comparative example 1, which contains cracks having a width and length of 120nm to 1000nm and 300nm to 2500nm and a purity of 65.1%, and preparing a lithium ion battery using the sample as a positive electrode material of a lithium battery, graphite as a negative electrode material of the lithium battery, and an ethyl carbonate solution of lithium hexafluorophosphate as an electrolyte, wherein the 4.5V first charge capacity of the battery is 313.6 mAh/g.
Comparative example 2
Taking 10kg of analytically pure nickel sulfate and 0.01g of analytically pure niobium pentachloride as raw materials to prepare 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container to react, filtering, washing and drying the precipitate to prepare a precursor 1, which is marked as Ni(1-x)Mex(OH)2Wherein Me is Nb and x is 10-5(ii) a Sintering in nitrogen atmosphere at 750 deg.C under 30bar pressure for 60min to obtain precursor 2, denoted as Ni(1-x)MexO, where Me is Nb and x is 10-5(ii) a Mixing the precursor 2 with Li in an equimolar ratio2Mixing O, sintering in nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to a median diameter D50 of 10 mu m, preparing a sample of comparative example 2, wherein the sample contains cracks, the width and length of the cracks are 250-1200 nm and 500-3000 nm, the purity of the sample is 60.3%, the sample is taken as a lithium battery anode material, graphite is taken as a lithium battery cathode material, and an ethyl carbonate solution of lithium hexafluorophosphate is taken as an electrolyte to jointly prepare a lithium ion battery, and the 4.5V primary charge capacity of the battery is 256.3 mAh/g.
Comparative example 3
Taking 10kg of analytically pure nickel sulfate as a raw material, preparing a 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container to react, filtering, washing and drying precipitates to prepare a precursor 1, which is recorded as Ni (OH)2(ii) a Sintering in a nitrogen atmosphere, wherein the pressure applied to sintering is 30bar, the sintering temperature is 750 ℃, and the sintering time is 60min, so as to prepare a precursor 2, and the precursor is recorded as NiO; adding 0.02g of inducing chemical tantalum bromide into the precursor 2, uniformly mixing, placing in a liquid nitrogen-196 ℃ environment for 60min, inducing the crystal structure under the cooperation of the low-temperature environment and the inducing chemical, and changing the grain size of the crystal structure to prepare a precursor 3; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to the median diameter D50 of 10 mu m, preparing a sample of a comparative example 3, wherein the sample contains cracks, the width and the length of the cracks are 500-2500 nm and 800-3500 nm, the purity of the sample is 55.6%, and a lithium ion battery prepared by taking the sample as a lithium battery anode material, graphite as a lithium battery cathode material and an ethyl carbonate solution of lithium hexafluorophosphate as an electrolyte, and the 4.5V primary charge capacity of the battery is 231.1 mAh/g.
Comparative example 4
Taking 10kg of analytically pure nickel sulfate as a raw material, preparing a 1mol/L sulfate solution, adding 5L of sulfate solution, 8L of 1mol/L sodium hydroxide solution and 0.2L of 10mol/L ammonia water into a reaction container to react, filtering, washing and drying precipitates to prepare a precursor 1, which is recorded as Ni (OH)2(ii) a Sintering in a nitrogen atmosphere, wherein the pressure applied to sintering is 30bar, the sintering temperature is 750 ℃, and the sintering time is 60min, so as to prepare a precursor 3, and the precursor is recorded as NiO; mixing the precursor 3 with Li in an equimolar ratio2Mixing O, sintering in nitrogen atmosphere, wherein the pressure for sintering is 40bar, the sintering temperature is 800 ℃, the sintering time is 80min, cooling to room temperature, crushing to the median diameter D50 of 10 mu m, preparing a sample of comparative example 4, the sample contains cracks, the width and length of the cracks are 200 nm-1800 nm and 600 nm-2200 nm, the purity of the sample is 67.4%, and a lithium ion battery and a battery prepared by using the sample as a lithium battery anode material, graphite as a lithium battery cathode material and an ethyl carbonate solution of lithium hexafluorophosphate as an electrolyte are used togetherThe 4.5V first charge capacity of the lithium ion secondary battery is 333.2 mAh/g.
The cracks of the examples or comparative examples were determined by scanning electron microscope SEM 3000.
The median particle diameter D50 of the example or comparative example samples was determined by a LS-909E laser particle size analyzer.
The BET specific surface area of the samples in examples or comparative examples was measured in accordance with GB/T19587-2017 "determination of solid matter specific surface area by BET method by gas adsorption".
The purity of the samples in the examples or comparative examples was calculated by fitting an X-ray diffractometer (D8 Advance) to xrd peak shapes.
In the lithium ion battery prepared by using the sample in the embodiment or the comparative example as the lithium battery positive electrode material, using graphite as the lithium battery negative electrode material and using the ethyl carbonate solution of lithium hexafluorophosphate as the electrolyte, the 4.5V first-time charge capacity of the battery is determined according to YS/T798-2012 LiCoMn.
Comparative examples 1 to 6 and comparative examples 1 to 4 were performed by measuring the specific surface area of the precursor 3, the purities of the pre-lithium material in examples 1 to 6 and the samples in comparative examples 1 to 4, and the first charge capacity under the condition that the charge voltage was 4.5V, respectively, and the results of the relevant test experiments are shown in Table 1
TABLE 1 comparative test results of examples and comparative examples
As can be seen from Table 1, the specific surface area of the precursor 3 in the examples 1 to 6 is much higher than that of the precursor 3 in the comparative examples 1 to 4, and the larger the specific surface area of the precursor 3 is, the more crack structures are, the more the preparation of the high-purity pre-lithium material is facilitated; from the purity experimental data of the examples 1 to 6 and the comparative examples 1 to 4, the experimental results are mutually verified, and the larger the specific surface area is, the higher the purity of the pre-lithium material is; in the method for preparing the pre-lithium material, the crystal structure is changed and the unit cell volume is further enlarged through the induction action of an induction environment or an induction chemical substance, lithium ions can be enabled to react with NiO more fully, so that segregation is reduced, the purity and the density of the pre-lithium material are improved, and the lithium removal capacity is further improved.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A high capacity lithium ion battery, comprising:
the chemical formula of the cathode material is LiNi(1-x)MexO, wherein x is 10-6～10-1Me is a third metal other than Li and Ni;
a negative electrode material; and
and (3) an electrolyte.
2. The lithium ion battery of claim 1, wherein the third metal is selected from one or two of Sr, Y, Nb, Ce, Ta, Mo, and W.
3. The lithium ion battery according to claim 1, wherein the positive electrode material has a crack, the width of the crack is 0.5nm to 1nm or 1nm to 100nm, and the length of the crack is 0.5nm to 1nm or 1nm to 500 nm.
4. The lithium ion battery of claim 1, wherein the lithium ion battery is characterized byThe positive electrode material has a median particle diameter D50 of 1 to 20 μm and a specific surface area of 0.1m2/g～100m2/g。
5. The lithium ion battery according to any one of claims 1 to 4, wherein the preparation method of the cathode material comprises the following steps:
s1, selecting nickel salt and an additive, and preparing a precursor 1 by adopting a chemical coprecipitation method;
s2, calcining the precursor 1 in an inert atmosphere to prepare a precursor 2;
s3, inducing the precursor 2 to induce a crack structure to prepare a precursor 3;
s4 mixing the precursor 3 with Li in an equal molar ratio2And O, mixing, sintering in an inert atmosphere, and crushing to prepare the cathode material.
6. The lithium ion battery according to claim 5, wherein in step S1, the nickel salt is selected from one or more of nickel sulfate, nickel nitrate, nickel chloride and nickel bromide.
7. The lithium ion battery of claim 5, wherein the additive comprises one or a mixture of two or more of compounds containing Sr, Y, Nb, Ce, Ta, Mo, or W.
8. The lithium ion battery of claim 5, wherein in step S3, the inducing operation is to be performed by placing in an inducing environment and/or adding an inducing chemical substance, wherein the inducing environment comprises one or more of a low temperature environment, a high pressure environment and a high temperature quenching environment.
9. The lithium ion battery of claim 8, wherein the low temperature environment is at a temperature of-100 ℃ to-250 ℃; the pressure of the high-pressure environment is 10-500 bar; the high-temperature quenching environment is that the steel plate is heated to 300-800 ℃ and then placed in liquid nitrogen to be cooled to room temperature; the inducing chemical substance is one or a mixture of more than two of Sr, Y, Nb, Ce, Ta, Mo or W compounds.
10. The lithium ion battery of claim 5, wherein the lithium ion battery has a 4.5V first charge capacity in excess of 410 mAh/g.
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