CN109860551B - Cobalt-nickel lithium ion battery positive electrode material and preparation method and application thereof - Google Patents
Cobalt-nickel lithium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a cobalt-nickel lithium ion battery anode material and a preparation method and application thereof, wherein the chemical general formula of the anode material is as follows: li x Co a Ni b R (1‑a‑b) O 2 Wherein: r is a doping element, R is selected from Mn, Y, Mg and/or Al, x is more than or equal to 0.9 and less than or equal to 1.1, a is more than or equal to 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.4, and a + b is more than or equal to 0.7 and less than or equal to 1; wherein the average length-diameter ratio of the positive electrode material is 1.5-3.0. The preparation method comprises the following steps: mixing raw materials containing a lithium source compound, a cobalt source compound, a nickel source compound and a doping element compound added according to needs according to a metering ratio, then adding a mixed solution consisting of an acidic substance and a solvent, further mixing, drying and sintering to obtain the cathode material. The invention omits the traditional precursor precipitation preparation process, and the prepared cobalt-nickel system anode material has uniform diffusion of lithium element and doping element, thereby improving the energy density, electrochemical performance and safety performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, mainly relates to the field of positive electrode materials for lithium ion batteries, and particularly relates to a cobalt-nickel lithium ion battery positive electrode material and a preparation method and application thereof.
Background
With the increasing demand of the information era for new battery materials and the strong demand of electronic products such as mobile phones, notebook computers, digital cameras, video cameras and the like and energy power products such as electric automobiles, electric tools and the like for novel, efficient and environment-friendly batteries, the market of lithium ion battery materials is continuously expanded. The positive electrode material is used as an important component of a lithium battery, the performance of the positive electrode material directly affects various performances of the battery, and the currently common positive electrode materials of the lithium ion battery mainly comprise lithium cobaltate, lithium manganate, lithium nickel cobalt manganese and lithium iron phosphate. Lithium cobaltate is mainly used in the field of 3C small-sized lithium ion batteries due to limited cobalt storage capacity and safety reasons, and lithium manganate and lithium iron phosphate materials are low in energy density and tend to be gradually replaced by nickel-containing materials with low cobalt content, such as lithium nickel manganese cobalt.
Cobalt-nickel binary and cobalt-nickel-manganese ternary materials (collectively referred to as nickel-cobalt or cobalt-nickel-based positive electrode materials) are generally layered rock salt structure materials, the content of nickel and manganese elements can be high or low, and manganese can be completely replaced by nickel. Cobalt (Co) is one of the main structural elements of the anode material, and the cobalt compound have high conductivity, so that the discharge capacity and high-rate discharge performance of the material can be improved. Nickel (Ni) is also one of the main active substances of the material, and can improve the capacity of the material, but the valence of Ni is changeable, and the capacity loss is large in the circulating process. Manganese (Mn) has good electrochemical inertia, and can enable the material to keep a stable structure all the time.
The performance of the nickel-cobalt anode material is closely related to the preparation method, and the preparation method comprises a plurality of methods, such as a high-temperature solid phase method, a coprecipitation method, a sol-gel method, a spray pyrolysis method and the like. The high-temperature solid phase method is a common method for preparing the anode material at present, and raw materials are directly mixed in a solid state form and synthesized at high temperature. The high-temperature solid phase method has simple process and is suitable for large-scale production, but the uniform mixing is difficult to ensure, so that the product batch consistency is poor and the electrochemical performance is unstable; the coprecipitation method is to mix chemical raw materials in a solution state, add a proper precipitator into the solution, coprecipitate the components which are uniformly mixed in the solution according to a stoichiometric ratio, or firstly react and precipitate an intermediate product in the solution, and then prepare the anode material by calcination. The coprecipitation method can control the shape and the granularity of the cobalt-nickel system precursor, is favorable for obtaining materials with stable shape, grain diameter and density after being synthesized with a lithium source by high-temperature solid phase, is the most main method for preparing the nickel-cobalt system anode material at present, but has high energy consumption by adopting a conventional multi-step sintering process in the production process, in the process of mixing and roasting the lithium source and the nickel-cobalt hydroxide precursor, because the lithium source is also a macroscopic particulate matter, the contact area and the distribution of the lithium source and the precursor are not uniform in the diffusion process, which may cause the non-uniformity of the local lithium source on the surface of the material, causing the high content of free lithium, and the same problem also exists in the process of surface doping and coating that the doping element is permeated/diffused to the surface and the bulk phase of the positive electrode material, so the problems of the distribution and the diffusion of the lithium source and the doping element on the surface of the precursor material need to be solved; the sol-gel method has complex process and higher cost, and the appearance and the grain diameter of the product are not easy to control; the spray pyrolysis method is limited to experimental research at present and can not realize industrialization.
Disclosure of Invention
The prior art has the problems that in the preparation process of the existing cobalt-nickel system cathode material, the uniformity of mixed materials is difficult to ensure in the cathode material prepared by a high-temperature solid phase method, so that the product batch consistency is poor, the electrochemical performance is unstable, the cathode material prepared by a coprecipitation method has the problems of non-uniform diffusion of a lithium source and a doping element, the content of free lithium is high, the energy consumption of a sintering process for preparing a precursor in the production process is high, and the safety of the prepared lithium ion battery is poor.
In order to solve the above technical problems, the inventors of the present invention have analyzed the cobalt-nickel based positive electrode material preparation process, and have found that, in the high temperature solid phase method for preparing the positive electrode material, the raw materials are not mixed in a solid state, but the raw materials are stirred in water and/or an isopropanol solvent to uniformly mix the components of the raw materials, but in the subsequent drying and evaporation of the solvent, the dried cobalt-nickel raw materials are still mixed unevenly due to different concentrations and diffusion rates, and thus the electrochemical performance is unstable. Therefore, the inventor creatively adds the mixed solution of water and an acid substance after physically mixing the raw materials to carry out chemical uniform mixing at normal temperature, the purpose of adding the acid substance is to dissolve/react the surfaces of the raw materials so as to more uniformly mix the raw materials, and simultaneously, the nonuniform mixed material caused in the solvent evaporation process is inhibited.
Specifically, the invention provides the following technical scheme:
a cobalt-nickel lithium ion battery positive electrode material has a chemical formula as follows: li x Co a Ni b R (1-a-b) O 2 Wherein: r is a doping element, R is selected from Mn, Y, Mg and/or Al, x is more than or equal to 0.9 and less than or equal to 1.1, a is more than or equal to 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.4, and a + b is more than or equal to 0.7 and less than or equal to 1; wherein the average length-diameter ratio of the positive electrode material is 1.5-3.0.
Preferably, in the above-described positive electrode material, the positive electrode material has an average aspect ratio of 1.7 to 2.5.
Preferably, in the positive electrode material, the pole piece compaction density of the positive electrode material is more than 3.6g/cm 3 Preferably 3.6 to 4.3g/cm 3 。
Preferably, in the positive electrode material, the positive electrode material is obtained by adding a mixed solution of an acidic substance and a solvent to a raw material containing a lithium source compound, a cobalt source compound, a nickel source compound, and, if necessary, a dopant element compound, followed by drying and sintering.
In the positive electrode material, the mass ratio of the mixed solution to the raw material is preferably 20 to 200:100, and more preferably 26 to 71: 100.
Preferably, in the positive electrode material, the solvent is deionized water and/or isopropanol, and the mass ratio of the acidic substance to the solvent in the mixed solution is 0.4-4:1, preferably 0.75-2.5: 1.
In the positive electrode material, the acidic substance is preferably a carboxylic acid, preferably one or two or more of formic acid, acetic acid, adipic acid, and citric acid, and more preferably acetic acid.
In the above positive electrode material, the lithium source compound is preferably one or two or more selected from the group consisting of lithium hydroxide monohydrate, lithium oxalate, lithium carbonate, lithium acetate, lithium tert-butoxide, and lithium citrate.
In the positive electrode material, the cobalt source compound is preferably one or more selected from cobalt (ii) carbonate, cobalt (ii) hydroxide, and cobalt (ii) oxide.
In the positive electrode material, the nickel source compound is preferably one or more selected from nickel (ii) carbonate, nickel (ii) hydroxide and nickel (ii) oxide.
In the positive electrode material, the doping element compound is preferably one or more selected from salts, hydroxides, oxides, and organic substances of manganese, yttrium, magnesium, and aluminum.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
mixing raw materials containing a lithium source compound, a cobalt source compound, a nickel source compound and a doping element compound added according to needs according to a metering ratio, then adding a mixed solution consisting of an acidic substance and a solvent, further mixing, drying and sintering to obtain the cobalt-nickel lithium ion battery anode material.
Preferably, in the preparation method, the drying temperature is 40-150 ℃, the drying pressure is 7-100kPa, and the drying time is 1.5-10 h.
Preferably, in the preparation method, the sintering temperature is 880-950 ℃, preferably, the sintering time is 10-20h, and more preferably, the sintering atmosphere is an oxygen atmosphere.
The invention also provides a lithium ion battery which comprises the cathode material.
The invention also provides application of the cathode material or the lithium ion battery in the field of lithium battery energy, preferably application in the fields of mobile communication equipment and electric vehicles.
The invention has the beneficial effects that:
(1) the invention physically mixes the raw materials of the cobalt-nickel anode material, adds the mixed liquid of water and acidic substances for chemical uniform mixing, and finally generates the anode material for the lithium ion battery under high-temperature sintering, the raw materials of the material are uniformly mixed, the internal and external structure lithium is uniform, the purposes of improving the energy density, the electrochemical performance and the safety performance of the lithium ion battery are achieved,
(2) the cobalt-nickel anode material of the invention is added with the doping elements in the raw material mixing stage, so that uniform dopants can be formed, the problem of non-uniform doping elements is solved, the electrochemical performance of the lithium ion battery is further improved, and the additional doping process is omitted.
(3) The cobalt-nickel anode material saves a precursor preparation process, saves energy consumption and has better application prospect.
Drawings
FIG. 1-a is a scanning electron micrograph of the positive electrode material of example 1, magnified 3000 times.
FIG. 1-b is a scanning electron micrograph of the positive electrode material of comparative example 1, magnified 3000 times.
FIG. 1-c is a scanning electron micrograph of the positive electrode material of example 2, at 3000 times magnification.
FIG. 1-d is a scanning electron micrograph of the positive electrode material of comparative example 2, magnified 3000 times.
FIG. 2 shows the 60 ℃ 0.5C/0.5C cycle results of cylindrical batteries prepared from the cathode materials of example 4, example 5, comparative example 4 and comparative example 5. Wherein 2-a, 2-b, 2-c, 2-d correspond to the cathode materials described in example 4, example 5, comparative example 4, comparative example 5, respectively.
Fig. 3 is a typical view of a nail penetration test of a cylindrical battery prepared from the positive electrode material of example 5 and comparative example 5. Wherein 3-a is the result of the nail penetration test of comparative example 5, and FIG. 3-b is the result of the nail penetration test of example 5.
Fig. 4 is a charge and discharge curve of a battery prepared from the cathode material of example 4.
Detailed Description
In the existing preparation process of the nickel-cobalt cathode material, the uniformity of mixed materials is difficult to ensure in the cathode material prepared by a high-temperature solid phase method, so that the batch consistency of products is poor, the electrochemical performance is unstable, the problem of uneven diffusion of a lithium source and doped elements exists in the cathode material prepared by a coprecipitation method, the content of free lithium is high, the energy consumption of a sintering process for preparing a precursor in the production process is high, and the safety of the prepared lithium ion battery is poor. In view ofThe invention provides a cobalt-nickel lithium ion battery positive electrode material, which has a chemical general formula as follows: li x Co a Ni b R (1-a-b) O 2 Wherein: r is a doping element, R is selected from Mn, Y, Mg and/or Al, x is more than or equal to 0.9 and less than or equal to 1.1, a is more than or equal to 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.4, and a + b is more than or equal to 0.7 and less than or equal to 1; wherein the average length-diameter ratio of the positive electrode material is 1.5-3.0.
In the cathode material, Co and Ni are main active structural substances, a stable reversible crystal structure of the cathode material is provided through the change of valence in charging and discharging, the charging and discharging cycle of the lithium ion battery is realized, and the doping element is selected from Mn, Y, Mg and/or Al, and the doping element has the main function of further stabilizing the structure of the cathode material and improving the contact between the cathode material and an electrolyte.
In a preferred embodiment of the present invention, the average aspect ratio of the positive electrode material is 1.7 to 2.5.
In a preferred embodiment of the present invention, the positive electrode material has a pole piece compacted density of greater than 3.6g/cm 3 Preferably 3.6 to 4.3g/cm 3 。
In a preferred embodiment of the present invention, the positive electrode material is obtained by adding a mixed solution of an acidic substance and a solvent to a raw material containing a lithium source compound, a cobalt source compound, a nickel source compound, and, if necessary, a dopant element compound, followed by drying and sintering.
Wherein the mass ratio of the mixed liquid to the raw materials is 20-200:100, preferably 26-71: 100.
Wherein the solvent is deionized water and/or isopropanol, and the mass ratio of the acidic substance to the solvent in the mixed solution is 0.4-4:1, preferably 0.75-2.5: 1.
Among them, the acidic substance is a carboxylic acid, preferably one or two or more of formic acid, acetic acid, adipic acid, and citric acid, and more preferably acetic acid.
Wherein the lithium source compound is one or more than two of lithium hydroxide monohydrate, lithium oxalate, lithium carbonate, lithium acetate, lithium tert-butoxide and lithium citrate.
Wherein the cobalt source compound is selected from one or more of cobalt (II) carbonate, cobalt (II) hydroxide or cobalt (II) oxide.
Wherein the nickel source compound is selected from one or more of nickel (II) carbonate, nickel (II) hydroxide or nickel (II) oxide.
Wherein the doping element compound is selected from one or more of manganese, yttrium, magnesium or aluminum salt, hydroxide, oxide or organic matter.
In a preferred embodiment of the present invention, the method for preparing the positive electrode material includes the steps of:
a) and (4) batching. Weighing a lithium source compound, a cobalt source compound, a nickel source compound and a doping element compound added according to needs, adding the mixture into a dispersing device, mixing, adding a mixed solution composed of an acidic substance and a solvent into the mixed material, stirring and dispersing uniformly, adding the uniformly dispersed material into a drying device, heating to 40-150 ℃, and performing vacuum drying for 1.5-10 hours under the vacuum degree of 7-100Kpa to prepare fluffy dry powder.
b) And (5) sintering. The dry powder prepared in the step a) is put into a ceramic bowl and is put into a sintering furnace, under the condition of introducing oxygen-enriched air, the temperature is raised to 880-950 ℃ at the speed of 5-15 ℃/min for sintering for 10-20h, and then the temperature is reduced and the material is discharged.
c) And (4) crushing. Crushing the material prepared in the step b) by a crusher to obtain the product of the invention.
The invention also provides a lithium ion battery which comprises an electrode made of the positive electrode material for the cobalt-nickel lithium ion battery.
The invention also provides application of the cathode material or the lithium ion battery in the field of lithium battery energy, preferably application in the fields of mobile communication equipment and electric vehicles.
The present invention will be described in further detail with reference to specific examples and comparative examples.
The reagent and apparatus information used in the examples and comparative examples are shown in tables 1 and 2.
TABLE 1 information on reagents used in examples of the invention and comparative examples
TABLE 2 information on the instruments used in the examples of the present invention and the comparative examples
Example 1
117.4kg of cobalt (II) carbonate, 6.4kg of nickel (II) carbonate, 12.7kg of yttrium nitrate hexahydrate, 1.6kg of nano aluminum hydroxide and 69.1kg of lithium carbonate are weighed and added into a high-speed dispersion machine lined with tungsten carbide to be uniformly mixed, and simultaneously, a mixed solution of 30.0kg of deionized water and 12.0kg of formic acid is weighed and slowly added into the high-speed dispersion machine lined with tungsten carbide, the mixture is dispersed at a high speed until the temperature is lower than 30 ℃, a rotary vacuum dryer is adopted, the prepared slurry is put into the high-speed dispersion machine and then heated to 40 ℃ for vacuum drying for 10 hours, and the vacuum degree is 8kPa, so that fluffy powdery gray material is obtained.
Adopting a 24m ventilation roller kiln, setting the temperature of a heating area to be 930 ℃, and introducing oxygen-enriched air (the volume ratio of oxygen content is 60 percent, and the gas input amount is 600 m) 3 And h), putting the dried material into a ceramic pot, sending the ceramic pot into a roller way for sintering, wherein the sintering time is 12h, isolating the material from air, cooling the material to normal temperature, weighing the weight of the material in and out, and counting the loss on ignition (the ratio of the mass difference of the sintering powder to the mass of the powder before sintering) to be 51.2%. Then, the cobalt-nickel positive electrode material is obtained by crushing with a super-micro crusher.
The particle size (D) of the positive electrode material prepared in this example was measured by a laser particle size analyzer v50 ) 10.2 μm; observed by electron microscope (SEM)Statistics shows that the average length-diameter ratio of the particles in the cathode material prepared in the embodiment is 3.0; the specific surface area of the cathode material prepared in this example is 0.25m detected by a specific surface area tester 2 /g。
The results of the quantitative analysis of the elements of the cathode material by ICP are shown in Table 3, and the structural formula of the cathode material prepared according to the Table 3 is Li 0.95 Co 0.90 Ni 0.05 Al 0.02 Y 0.03 O 2 。
Table 3 elemental characterization results for positive electrode materials described in example 1
| Element(s) | Li | Co | Ni | Mn | Al | Ca | Mg |
| Mass ratio of | 6.595 | 53.04 | 2.35 | 0.007 | 0.0548 | 0.0020 | 0.0024 |
| Atomic weight | 6.94 | 58.93 | 58.69 | 54.94 | 26.98 | 40.00 | 24.00 |
| Number of moles | 0.95 | 0.90 | 0.048 | 0.0001 | 0.02 | 0.00005 | 0.00010 |
| Element(s) | Na | P | S | Ti | Y | Zn | Zr |
| Mass ratio of | 0.0037 | 0.0047 | 0.0547 | 0.0398 | 2.67 | 0.0000 | 0.0023 |
| Atomic weight | 23.00 | 30.97 | 32.00 | 40.00 | 88.91 | 65.41 | 91.22 |
| Number of moles | 0.00016 | 0.00015 | 0.00171 | 0.0001 | 0.03 | 0.00000 | 0.00003 |
Example 2
Weighing 71.4kg of cobalt (II) carbonate, 52.8kg of nickel (II) carbonate, 0.2kg of manganese (II) oxalate dihydrate, 0.4kg of magnesium oxide and 75.7kg of lithium carbonate, adding the mixture into a plow rake type mixer, uniformly mixing, meanwhile, weighing a mixed solution of 80kg of deionized water and 320kg of acetic acid, slowly adding the mixed solution into the plow rake type mixer, dispersing at a high speed until the temperature is lower than 30 ℃, adopting a rotary vacuum dryer, putting the prepared slurry, heating to 150 ℃, and carrying out vacuum drying for 1.5 hours at the vacuum degree of 86kPa to prepare a fluffy powdery gray material for later use.
A24 m ventilated roller kiln is adopted. Setting the temperature of the heating zone to 880 ℃, and introducing oxygen-enriched air (the volume ratio of oxygen content is 60 percent, and the gas input is 500 m) 3 And h), putting the dried materials into a ceramic pot, sending the ceramic pot into a roller way for sintering, wherein the sintering time is 16h, isolating the materials from air, cooling the materials to normal temperature, weighing the weight of the materials in and out, and counting the loss on ignition (the ratio of the mass difference of the sintering powder to the mass of the powder before sintering)Value) was 49.2%. Then crushing by a vortex crusher to obtain the cobalt-nickel anode material.
The particle size (D) of the cathode material prepared in this example was measured v50 ) 7.0 μm, an average aspect ratio of the particles of 1.5, and a specific surface area of 0.5m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by quantitative analysis of the elements of the anode material by ICP is Li 1.01 Co 0.5 5 Ni 0.39 Mn 0.05 Mg 0.01 O 2 。
Table 4 elemental characterization results for the positive electrode materials described in example 2
| Element(s) | Li | Co | Ni | Mn | Al | Ca | Mg |
| Mass ratio of | 7.01 | 32.62 | 23.15 | 2.69 | 0.0021 | 0.0020 | 0.29 |
| Atomic weight | 6.94 | 58.93 | 58.69 | 54.94 | 26.98 | 40.00 | 24.00 |
| Number of moles | 1.01 | 0.55 | 0.39 | 0.049 | / | / | 0.012 |
| Element(s) | Na | P | S | Ti | Y | Zn | Zr |
| Mass ratio of | 0.0091 | 0.0027 | 0.0469 | 0.0086 | 0.0004 | 0.0000 | 0.0033 |
| Atomic weight | 23.00 | 30.97 | 32.00 | 40.00 | 88.91 | 65.41 | 91.22 |
| Number of moles | / | / | 0.0015 | / | / | / | / |
Example 3
Weighing 103.5kg of cobalt (II) carbonate, 19.7kg of nickel (II) carbonate, 3.3kg of nano aluminum hydroxide and 76.2kg of lithium carbonate, adding the mixture into a plow-rake mixer, uniformly mixing, weighing about 30kg of adipic acid, 30kg of citric acid, 40kg of deionized water and 40kg of isopropanol to prepare a mixed solution, slowly adding the mixed solution into the plow-rake mixer under stirring, heating to 60 ℃, stirring and dispersing for 60min, adding the prepared slurry into a rotary vacuum dryer, then heating to 110 ℃, and carrying out vacuum drying for 4h at a vacuum degree of 98kPa to prepare a fluffy powdery gray material for later use.
A24 m ventilated roller kiln is adopted. Setting the temperature of the heating zone to 920 ℃, and introducing oxygen-enriched air (the volume ratio of oxygen content is 80%, and the gas input quantity is 300 Nm) 3 H), putting the dried materials into a ceramic bowl, sending the ceramic bowl into a roller way for sintering, wherein the sintering time is 16h, isolating the materials from air, cooling the materials to normal temperature, and weighing the weight of the materials in and outThe statistical loss on ignition (the ratio of the mass difference of the sintered powder to the mass of the powder before sintering) was 51.1%. Then crushing by a vortex flow crusher to obtain the cobalt-nickel system anode material.
The particle size (D) of the cathode material prepared in this example was measured v50 ) 9.0 μm, an average aspect ratio of the particles of 2.2, and a specific surface area of 0.3m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by using ICP to carry out quantitative analysis on the elements of the anode material is Li 1.02 Co 0.8 Ni 0.15 Al 0.05 O 2 。
Example 4
85.7kg of cobalt (II) carbonate, 14.7kg of nickel (II) hydroxide, 5.5kg of magnesium oxide and 71.4kg of lithium carbonate are weighed and added into a high-speed dispersion machine lined with tungsten carbide to be uniformly mixed, and meanwhile, a mixed solution of 36kg of isopropanol and 90kg of acetic acid is weighed and slowly added into the high-speed dispersion machine to be dispersed at a high speed until the temperature is lower than 30 ℃. And (3) putting the prepared slurry into a rotary vacuum dryer, heating to 110 ℃, carrying out vacuum drying for 3.0h under the vacuum degree of 7kPa, and drying to obtain fluffy powdery gray materials for later use.
A24 m ventilated roller kiln is adopted. Setting the temperature of the heating zone at 950 deg.C, and introducing oxygen-enriched air (oxygen content volume ratio of 80%, gas input of 420 Nm) 3 And h), putting the dried materials into a ceramic pot, sending the ceramic pot into a roller way for sintering, wherein the sintering time is 10h, isolating the materials from air, cooling the materials to normal temperature, weighing the weight of the materials in and out, and counting the loss on ignition (the ratio of the mass difference of the sintering powder to the mass of the powder before sintering) to be 60.5%. Then crushing by a vortex crusher to obtain the cobalt-nickel anode material.
The particle size (D) of the cathode material prepared in this example was measured v50 ) 11.0 μm, the average aspect ratio of the particles was 2.5, and the specific surface area was 0.2m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by using ICP to carry out quantitative analysis on the elements of the anode material is Li 1.01 Co 0.70 Ni 0.15 Mg 0.15 O 2 。
Example 5
87.1Kg of cobalt (II) carbonate, 19.0Kg of nickel (II) carbonate, 12.2Kg of magnesium carbonate and 28.6Kg of lithium hydroxide monohydrate are weighed and added into a high-speed dispersion machine lined with tungsten carbide to be uniformly mixed, and simultaneously, a mixed solution of 9.2Kg of water, 8.2Kg of isopropanol and 21.2Kg of acetic acid is weighed and slowly added into the high-speed dispersion machine to be dispersed at a high speed until the temperature is lower than 30 ℃. And (3) putting the prepared material into a rotary vacuum dryer, heating to 110 ℃, and carrying out vacuum drying for 4h at the vacuum degree of 8kPa to obtain fluffy powdery gray material for later use.
A24 m vented pusher kiln was used. Setting the temperature of the heating area to 920 ℃, and introducing oxygen-enriched air (the volume ratio of oxygen content is 80 percent, and the gas input amount is 500 Nm) 3 And h), putting the dried materials into a ceramic bowl, sending the ceramic bowl into a kiln for sintering, wherein the sintering time is 20h, isolating the materials from air, cooling the materials to normal temperature, weighing the weight of the materials in and out, and counting the loss on ignition (the ratio of the mass difference of the sintering powder to the mass of the powder before sintering) to be 32.2%. Then crushing by a vortex crusher to obtain the cobalt-nickel anode material.
The particle size (D) of the cathode material prepared in this example was measured v50 ) 9.6 μm, an average aspect ratio of the particles of 1.7 and a specific surface area of 0.4m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by quantitative analysis of the elements of the anode material by ICP is Li 1.04 Co 0.70 Ni 0.15 Mg 0.15 O 2 。
Comparative example 1
The commercial precursor Co 0.90 Ni 0.05 Al 0.02 Y 0.03 (OH) 2 95.4kg of the positive electrode material was weighed and charged into a high-speed disperser, and 37.9kg of lithium carbonate was further weighed and mixed in the high-speed disperser, and the cobalt-nickel-based positive electrode material was prepared under the same preparation conditions as in example 1, and the statistical loss on ignition (the ratio of the mass difference of the sintered powder to the mass of the powder before sintering) was 25.2%.
Through detection, the granularity (D) of the cobalt-nickel cathode material obtained in the comparative example 1 v50 ) 19.2 μm, an average aspect ratio of the particles of 4.0, a specific surface area of 0.4m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by using ICP to carry out quantitative analysis on the elements of the anode material is Li 0.95 Co 0.90 Ni 0.05 Al 0.02 Y 0.03 O 2 。
Comparative example 2
Mixing a commercial precursor Co 0.55 Ni 0.39 Mn 0.05 Mg 0.01 (OH) 2 89.9kg of the powder was weighed and added to a plow and rake mixer, and 44.3kg of lithium hydroxide monohydrate was added and mixed in the plow and rake mixer, and the cobalt-nickel based positive electrode material was prepared under the same preparation conditions as in example 2, and the statistical loss on ignition (the ratio of the mass difference of the sintered powder to the mass of the powder before sintering) was 25.6%.
Through detection, the granularity (D) of the nickel-cobalt cathode material obtained in the comparative example 2 v50 ) 6.7 μm, an average aspect ratio of the particles of 1.0, and a specific surface area of 0.6m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by using ICP to carry out quantitative analysis on the elements of the anode material is Li 1.01 Co 0.5 5 Ni 0.39 Mn 0.05 Mg 0.01 O 2 。
Comparative example 3
Comparative example 3 and inventive example 3 were the same in raw materials and preparation method, except that the mixed solution of comparative example 3 was 15kg of adipic acid, 15kg of citric acid, 2kg of deionized water and 3kg of isopropyl alcohol.
The particle size (D) of the cobalt-nickel positive electrode material obtained in comparative example 3 was examined v50 ) 9.3 μm, an average aspect ratio of the particles of 1.1, and a specific surface area of 0.4m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by using ICP to carry out quantitative analysis on the elements of the anode material is Li 1.02 Co 0.8 Ni 0.15 Al 0.05 O 2 。
Comparative example 4
Comparative example 4 is the same as example 4 of the present invention in terms of raw materials and preparation method except that the mixed solution of comparative example 4 is 270kg of isopropyl alcohol and 90kg of acetic acid.
Through detection, the granularity of the cobalt-nickel anode material obtained in the comparative example 4(D v50 ) 7.5 μm, an average aspect ratio of the particles of 1.3, and a specific surface area of 1.32m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by quantitative analysis of the elements of the anode material by ICP is Li 1.01 Co 0.70 Ni 0.15 Mg 0.15 O 2 。
Comparative example 5
Comparative example 5 and inventive example 5 were made from the same starting materials and in the same manner except that no water was added to the mixture of comparative example 5.
Through detection, the granularity (D) of the cobalt-nickel cathode material obtained in the comparative example 5 v50 ) 8.9 μm, an average aspect ratio of the particles of 1.1 and a specific surface area of 0.3m 2 /g。
The structural formula of the synthesized multi-element solid solution obtained by using ICP to carry out quantitative analysis on the elements of the anode material is Li 1.04 Co 0.70 Ni 0.15 Mg 0.15 O 2 。
Table 5 elemental characterization results of the positive electrode material described in comparative example 5
| Element(s) | Li | Co | Ni | Mn | Al | Ca | Mg |
| Mass ratio of | 7.21 | 41.72 | 9.27 | 0.007 | 0.0020 | 0.0025 | 3.58 |
| Atomic weight | 6.94 | 58.93 | 58.69 | 54.94 | 26.98 | 40.00 | 24.00 |
| Number of moles | 1.04 | 0.708 | 0.158 | / | / | / | 0.149 |
| Element(s) | Na | P | S | Ti | Y | Zn | Zr |
| Mass ratio of | 0.0068 | 0.0028 | 0.0462 | 0.0057 | 0.003 | 0.0000 | 0.000 |
| Atomic weight | 23.00 | 30.97 | 32.00 | 40.00 | 88.91 | 65.41 | 91.22 |
| Number of moles | / | / | 0.0014 | / | / | / | / |
The positive electrode materials prepared in the above examples and comparative examples were subjected to the following characterization:
1. SEM image
The positive electrode material powders prepared in example 1, comparative example 1, example 2 and comparative example 2 were subjected to SEM test (magnification Mag ═ 3.00KX, ZEISS) by scanning electron microscopy, respectively, to obtain the results of fig. 1-a,1-b,1-c, 1-d.
As can be seen from figures 1-a and 1-b, the particle size of comparative example 1 is much larger than that of example 1, the surface is rough, the surface of example 1 is uniformly coated with a layer of light-colored substance, the surface of the particle is smooth, and the sphericity is good.
As can be seen from fig. 1-c and 1-d, a plurality of small particles exist among the particles in comparative example 2, the particle size is much larger than that in example 2, and the morphology of the secondary spherical particles is still maintained in example 2, which indicates that the growth differentiation of the particles of the cathode material prepared by the method is inhibited, and the sphericity degree of the particles is better and more uniform. The performance of the lithium ion secondary battery prepared in the later period is improved.
2. Free lithium and pH value
About 50g of each of the positive electrode materials prepared in example 1, example 2, comparative example 1 and comparative example 2 was taken, and the free lithium content and pH value in the invention were measured by a leaching titration method. The specific operation is as follows: 50g of the positive electrode material (code m, unit g) was taken, about 100g of deionized water was added, stirred on a magnetic stirrer for 30min, filtered by filter paper, and 50ml of the liquid was weighed by a pipette (50ml) and placed in a 100ml beaker with a magnetic stirrer. The beaker was placed on an auto titrator lined with white round filter paper and 2 drops of phenolphthalein indicator (0.1g/L absolute ethanol solution) were added dropwise, typically at this point the solution was pink.
Titration was started with hydrochloric acid standard liquid (0.049mol/L, code C, unit mol/L) and when the solution turned from red to colorless, the volume V of hydrochloric acid solution consumed was recorded 1 (unit: ml). 2 drops of methyl red (0.1g/L absolute ethanol solution) indicator were added dropwise to the solution and titration of the hydrochloric acid solution was continued until the color of the solution changed from yellow to orange.
Taking out the beaker, boiling and heating to evaporate carbon dioxide generated in the solution, and cooling to return the solution to be yellow. The beaker was removed and cooled to room temperature (23. + -. 2 ℃ C.) and the titration of the solution was continued, and when the solution changed from yellow to pale red, the volume V of the hydrochloric acid standard solution was recorded 2 (unit: ml). The calculation formula of the leaching solution converted into the content of free lithium carbonate and lithium hydroxide in the cathode material is as follows.
Li 2 CO 3 (wt％)＝(V 2 -V 1 )*C*73.886*2*100/1000/m
LiOH(wt％)＝[V 2 -2*(V 2 -V 1 )]*C*23.946*2*100/1000/m
Li + (wt％)＝V 2 *C*6.94*2*100/m/1000
Reference GB/T9724-2007, 45g of deionized water was added into 5g of samples of the examples, the samples were stirred and stirred for 30min by clean magnetic force, then the samples were left to stand for 90min and filtered by filter paper, the clear filtrate was taken and tested for pH value by a pH meter at 23 + -2 ℃ to obtain the pH value of the powders of the examples, and the results of the free lithium and the pH value of the above examples are shown in Table 6.
Table 6 examples free lithium content and pH test results
| Examples | Lithium hydroxide | Lithium carbonate | Total free lithium | pH value |
| Unit | (wt％) | (wt％) | (wt％) | --- |
| Example 1 | 0.0300 | 0.0100 | 0.0100 | 10.31 |
| Example 2 | 0.0377 | 0.0737 | 0.0435 | 10.27 |
| Comparative example 1 | 0.1671 | 0.0428 | 0.2330 | 10.65 |
| Comparative example 2 | 0.0847 | 0.0930 | 0.0985 | 10.75 |
As can be seen from table 6, the residual lithium and pH values in examples 1 and 2 are lower than those in comparative examples 1 and 2, and the residual lithium generally refers to a lithium compound remaining on the surface and in the particles of the solid powder due to incomplete reaction, and is usually present in the form of lithium hydroxide or lithium carbonate, and the lithium hydroxide powder can absorb carbon dioxide and convert into lithium carbonate when exposed to air. When the residual lithium is brought into the lithium ion battery, the residual lithium reacts with the electrolyte to generate gas in the formation stage of the lithium battery, and meanwhile, the unreacted lithium carbonate and the residual substance after the reaction with the electrolyte also continuously generate gas or weaken the performance of the lithium ion battery, so that the residual lithium is avoided as much as possible in the synthesis process of the cathode material. Therefore, the results show that the preparation process of the precursor is omitted, the process for directly synthesizing the cobalt-nickel anode material by adopting the raw material compound is feasible, and the synthesis reaction is complete.
3. Full cell preparation and performance evaluation
The positive electrode material powder prepared in the examples and the comparative examples is used as a positive electrode active substance to prepare a power battery with the capacity of about 4.8-5.2Ah according to the 21700 cylindrical battery design, and the cylindrical battery is taken as a standard when the cylindrical battery is designed to have the same capacity margin (namely, the volume occupied by the active substance in the cylindrical battery and the total closed effective volume percentage of the cylindrical battery are about 96 percent generally). The full battery is manufactured and mainly used for inspecting the circulation and safety effects of the lithium battery. The variety evaluated to be suitable is a 21700-coiled steel shell battery, and the diameter of the manufactured battery is 21mm, and the height of the manufactured battery is 71 mm.
Meanwhile, the size of the 21700 single battery is fixed, for example, the compaction density of the positive and negative pole pieces can be improved, and under the condition of a certain designed volume ratio, more active substances can be arranged in the positive and negative pole pieces, so that the apparent energy of the lithium battery can be improved, and the direct effect of improving the energy density of the lithium battery is brought. The design of lithium batteries is typically based on the compacted density of the pole pieces.
The positive pole piece is prepared by preparing slurry, coating, cold pressing, slitting and the like, the content of the effective positive active substance in the pole piece is 97.5 percent, and the average coating weight of the pole piece is 0.0260g/cm 3 The coating width of the pole piece is 62mm, and the total area of the active substances of the pole piece is 937.4cm 2 The aluminum foil substrate had a thickness of 13 μm, and the compacted densities of the electrode sheets prepared from the powders of the positive electrode materials of the examples and comparative examples were as shown in table 7 below. As can be seen from table 7, after the anode material with the same atomic ratio of elements changes the appropriate length-diameter ratio of the particles, the compacted density of the electrode sheet prepared from the material is greatly increased (3% to 13.5%), and the compacted density of the NCA material is particularly significantly increased (13.2%), which may be due to the fact that the compactness of the structure of the material prepared with a certain length-diameter ratio is improved to a certain extent, and the orientation of the material is significant when the electrode sheet is prepared, thereby being beneficial to improving the compacted density of the electrode sheet, and being capable of effectively improving the energy density per unit volume or unit weight of the lithium battery on the basis of ensuring the electrochemical performance of the material.
TABLE 7 example Pole piece compaction Density
| Examples | Pole piece compaction density (g/cm) 3 ) |
| Example 1 | 4.25 |
| Example 2 | 3.9 |
| Example 3 | 3.6 |
| Example 4 | 4.1 |
| Example 5 | 4.05 |
| Comparative example 1 | 3.95 |
| Comparative example 2 | 3.61 |
| Comparative example 3 | 3.18 |
| Comparative example 4 | 3.71 |
| Comparative example 5 | 3.58 |
The preparation method of the cathode plate generally comprises the steps of preparing slurry, coating, cold pressing, slitting and the likeAnd (5) preparing. When the artificial graphite is used as the negative active material, the content of the prepared pole piece effective negative active material (artificial graphite) is 96.0 percent, and the coating weight of the pole piece is 0.0164g/cm 2 The coating width of the pole piece is 63.5mm, and the total area of the active substances of the pole piece is 1009.65cm 2 The thickness of the copper foil base material is 9 mu m, and the compacted density of the pole piece is 1.65g/cm calculated by active substances 3 。
The method comprises the steps of sequentially winding a positive plate welded with an aluminum lug, an isolation film (a PP/PE/PP composite isolation film which is not treated by nano aluminum oxide and has the thickness of 16 mu m), a negative plate welded with a nickel lug and the like to prepare a cylindrical bare cell, sleeving the lug on an insulating ring, putting the lug into a shell, welding the nickel lug at the bottom of a cylinder by laser welding, then curling to prepare the bare cell with a groove, drying, cooling, injecting liquid, sequentially welding protective members such as CID, PTC and Vent on the lug, packaging, standing, forming by a high-temperature forming machine of an LIP-10AHB06 type (forming voltage of 0-4.2V, charging at 0.1C, discharging at 0.2C and temperature of 45 +/-2 ℃), carrying out capacity testing (testing voltage of 3.0-4.2V, 0.2C and 0.5C), and selecting qualified cells for subsequent performance evaluation.
Lithium batteries prepared from the positive electrode materials of example 4, example 5, comparative example 4 and comparative example 5 were placed in an oven at 60 ℃, and the electrodes were connected to a high temperature forming machine of the LIP-10AHB06 type for 1C/1C, 3.0-4.2V cycle test, so as to obtain the high temperature cycle results of FIG. 2, wherein curves 2-a, 2-b, 2-C and 2-d correspond to the lithium batteries prepared from the positive electrode materials of example 4, example 5, comparative example 4 and comparative example 5, respectively. As can be seen from fig. 2, the lithium ion batteries prepared from the cathode materials of examples 4 and 5 of the present invention have excellent cycle performance, and the cycle capacity retention rate is still greater than 90% after 300 cycles, while the lithium ion batteries prepared from the cathode materials of comparative examples 4 and 5 have relatively smooth early cycle, water jump starts immediately after about 250 cycles, and the internal resistance of the corresponding lithium ion battery starts to increase, which indicates that an unknown side reaction occurs inside the lithium battery to cause rapid capacity fading, and the related reasons need further anatomical analysis.
4. Button cell preparation and performance evaluation
Weighing 70g of N-methyl pyrrolidone (NMP) into a container of a dispersion machine for experiments, starting stirring, adding 5g of polyvinylidene fluoride (PVDF Solef6020) powder under the stirring condition, weighing 5g of conductive carbon powder (SP) into the solution after the adhesive is completely dissolved, adding 90g of the final crushed material prepared in example 4 into the solution after high-speed dispersion for 60min, reducing the stirring speed after dispersion for 1-1.5 h, and discharging for later use.
And taking an aluminum foil with the thickness of 16 mu m as a current collector, uniformly coating the prepared slurry on the aluminum foil, and drying in a drying oven at the baking temperature of 105 ℃ for 1h to prepare the positive plate.
The prepared positive plate is compacted, the compacted density of the active material of the plate is 3.3g/cm3, the thickness of the active material is about 85 μm, and the total thickness is about 100 μm. And meanwhile, preparing a CR 2032 type button cell by taking the compacted positive plate, taking a metal lithium plate (Tianjin product, 99.9%) as a counter electrode and LBC301 as an electrolyte, and standing for 6-10 h after electricity deduction. At normal temperature, a 2000-type battery test system (produced by Wuhan) is used for carrying out capacity test on the battery, the charge-discharge flow is 3.0-4.35V, the charge-discharge multiplying power is 0.1C, and the corresponding current density is 1mA/cm 2 The results of FIG. 4 were obtained.
As can be seen from fig. 4, the specific capacity of the cathode material prepared in example 4 is 169, two discharge platforms of 3.88V and 3.56V exist in a discharge curve, the discharge curve is gentle, the coulombic efficiency is greater than 98%, and 2 platforms also exist in a corresponding charge curve, which indicates that the prepared material has a complete structure and good reversibility.
5. Safety nail penetration test
The 21700 cylindrical lithium ion secondary battery prepared by the positive electrode materials of the embodiment 1, the embodiment 4, the embodiment 5, the embodiment 4 and the embodiment 5 is nailed (nail diameter phi 8mm, puncture speed is 20-25 mm/s) according to QC/T743-2006 (lithium ion storage battery for electric road vehicle), overcharging (constant current charging to 200% rated capacity) is tested, 2-3 detected qualified lithium battery cells are taken out from each group, the temperature is kept for 2h under the room temperature condition (23 ℃ +/-2 ℃), then the battery cells are discharged to 3.0V according to 0.5C on a LIP-10AHB06 type high temperature formation machine, the discharging is finished and the standing is carried out for 30s, the battery cells are taken out to detect the indexes of the thickness, the internal resistance and the like, then the battery cells are put on a rack to be charged to 4.2V according to 0.5C again, then the battery cells are taken out to be charged to 4.2V according to the cutoff voltage through the small current CV of 20mA, the thickness and the terminal voltage and the internal resistance are taken out again, the cells were then allowed to stand for 2 hours and tested as standard to give representative results as shown in FIG. 3-a (comparative example 5), FIG. 3-b (example 5) and Table 8.
TABLE 8 results of nail penetration test in examples
As can be seen from fig. 3-a and 3-b, the lithium batteries prepared in example 5 and comparative example 5 according to the present invention all passed the nail prick abuse condition, and the temperature rise was not significant, but the lithium battery prepared in comparative example 5 had a higher temperature rise than example 5 during the test and the voltage dropped directly to zero, indicating that some protection structures may be in operation during the test. Meanwhile, as can be seen from table 7, the internal resistance of the cell of comparative example 5 sharply increases after the test, and the service condition as a reversible lithium ion battery has been practically lost. Therefore, the nail penetration test can work through the components of the cylindrical battery, and the material prepared in the comparative example 5 has larger safety risk in the using process.
While specific embodiments of the invention have been described with reference to the above examples, it will be understood by those skilled in the art that the examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention, which is to be given the full breadth of the appended claims, as defined in the appended claims, and any and all changes that come within the meaning and range of equivalents thereof may be embraced by the following claims.
Claims (43)
1. The positive electrode material of the cobalt-nickel lithium ion battery is characterized in that the chemical general formula of the positive electrode material is as follows: li x Co a Ni b R (1-a-b) O 2 Wherein: r is a doping element, R is selected from Mn, Y, Mg and/or Al, x is more than or equal to 0.9 and less than or equal to 1.1, a is more than or equal to 0.55 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.4, and a + b is more than or equal to 0.7 and less than or equal to 1; wherein the average length-diameter ratio of the positive electrode material is 1.5-3.0;
the cathode material is prepared by adding a mixed solution consisting of an acidic substance and a solvent into a raw material containing a lithium source compound, a cobalt source compound, a nickel source compound and a doping element compound added according to needs, drying and sintering;
the acidic substance is a carboxylic acid and the acidic substance is,
the carboxylic acid is one or more than two of formic acid, acetic acid, adipic acid or citric acid;
the solvent is deionized water and/or isopropanol, and the mass ratio of the acidic substance to the solvent in the mixed solution is 0.4-4: 1.
2. The positive electrode material according to claim 1, wherein the average aspect ratio of the positive electrode material is 1.7 to 2.5.
3. The positive electrode material of claim 1, wherein the positive electrode material has a pole piece compacted density of greater than 3.6g/cm 3 。
4. The positive electrode material according to claim 1, wherein the positive electrode material has a pole piece compacted density of 3.6-4.3g/cm 3 。
5. The positive electrode material of claim 2, wherein the positive electrode material has a pole piece compacted density of greater than 3.6g/cm 3 。
6. The positive electrode material according to claim 1, wherein the mass ratio of the mixed solution to the raw material is 20-200: 100.
7. The positive electrode material according to claim 2, wherein the mass ratio of the mixed solution to the raw material is 20-200: 100.
8. The positive electrode material according to claim 3, wherein the mass ratio of the mixed solution to the raw material is 20-200: 100.
9. The positive electrode material according to claim 1, wherein the mass ratio of the mixed solution to the raw material is 26-71: 100.
10. The positive electrode material according to any one of claims 1 to 9, wherein a mass ratio of the acidic substance to the solvent in the mixed solution is 0.75 to 2.5: 1.
11. The positive electrode material according to any one of claims 1 to 9, wherein the acidic substance is acetic acid.
12. The positive electrode material according to any one of claims 1 to 9, wherein the lithium source compound is one or two or more selected from lithium hydroxide monohydrate, lithium oxalate, lithium carbonate, lithium acetate, lithium tert-butoxide, and lithium citrate.
13. The positive electrode material according to claim 10, wherein the lithium source compound is one or more selected from lithium hydroxide monohydrate, lithium oxalate, lithium carbonate, lithium acetate, lithium tert-butoxide, and lithium citrate.
14. The positive electrode material according to claim 11, wherein the lithium source compound is one or more selected from lithium hydroxide monohydrate, lithium oxalate, lithium carbonate, lithium acetate, lithium tert-butoxide, and lithium citrate.
15. The positive electrode material according to any one of claims 1 to 9, wherein the cobalt source compound is one or more selected from cobalt (ii) carbonate, cobalt (ii) hydroxide, and cobalt (ii) oxide.
16. The positive electrode material according to claim 10, wherein the cobalt source compound is one or more selected from cobalt (ii) carbonate, cobalt (ii) hydroxide and cobalt (ii) oxide.
17. The positive electrode material according to claim 11, wherein the cobalt source compound is one or more selected from cobalt (ii) carbonate, cobalt (ii) hydroxide and cobalt (ii) oxide.
18. The positive electrode material according to claim 12, wherein the cobalt source compound is one or more selected from cobalt (ii) carbonate, cobalt (ii) hydroxide and cobalt (ii) oxide.
19. The positive electrode material according to any one of claims 1 to 9, wherein the nickel source compound is one or more selected from nickel (ii) carbonate, nickel (ii) hydroxide, and nickel (ii) oxide.
20. The positive electrode material according to claim 10, wherein the nickel source compound is one or more selected from the group consisting of nickel (ii) carbonate, nickel (ii) hydroxide and nickel (ii) oxide.
21. The positive electrode material according to claim 11, wherein the nickel source compound is one or more selected from nickel (ii) carbonate, nickel (ii) hydroxide, and nickel (ii) oxide.
22. The positive electrode material according to claim 12, wherein the nickel source compound is one or more selected from the group consisting of nickel (ii) carbonate, nickel (ii) hydroxide, and nickel (ii) oxide.
23. The positive electrode material according to claim 15, wherein the nickel source compound is one or more selected from the group consisting of nickel (ii) carbonate, nickel (ii) hydroxide and nickel (ii) oxide.
24. The positive electrode material according to any one of claims 1 to 9, wherein the doping element compound is one or more selected from salts, hydroxides, oxides, and organics of manganese, yttrium, magnesium, and aluminum.
25. The positive electrode material according to claim 10, wherein the dopant element compound is one or more selected from a salt, a hydroxide, an oxide, and an organic substance of manganese, yttrium, magnesium, and aluminum.
26. The positive electrode material according to claim 11, wherein the doping element compound is one or two or more selected from a salt, a hydroxide, an oxide, and an organic substance of manganese, yttrium, magnesium, or aluminum.
27. The positive electrode material according to claim 12, wherein the dopant element compound is one or more selected from a salt, a hydroxide, an oxide, and an organic substance of manganese, yttrium, magnesium, and aluminum.
28. The positive electrode material according to claim 15, wherein the dopant element compound is one or more selected from a salt, a hydroxide, an oxide, and an organic substance of manganese, yttrium, magnesium, and aluminum.
29. The positive electrode material according to claim 19, wherein the doping element compound is one or two or more selected from a salt, a hydroxide, an oxide, and an organic substance of manganese, yttrium, magnesium, or aluminum.
30. The method for preparing a positive electrode material for a cobalt-nickel lithium ion battery according to any one of claims 1 to 29, comprising the steps of:
mixing raw materials containing a lithium source compound, a cobalt source compound, a nickel source compound and a doping element compound added according to needs according to a metering ratio, then adding a mixed solution consisting of an acidic substance and a solvent, further mixing, drying and sintering to obtain the cobalt-nickel lithium ion battery anode material.
31. The method according to claim 30, wherein the drying temperature is 40 to 150 ℃.
32. The production method according to claim 30, wherein the drying pressure is 7 to 100 kPa.
33. The production method according to claim 31, wherein the drying pressure is 7 to 100 kPa.
34. The method according to claim 30, wherein the drying time is 1.5 to 10 hours.
35. The method of claim 31, wherein the drying time is 1.5 to 10 hours.
36. The method according to claim 32, wherein the drying time is 1.5 to 10 hours.
37. The preparation method according to any one of claims 30 to 36, wherein the sintering temperature is 880-950 ℃.
38. The production method according to any one of claims 30 to 36, wherein the sintering time is 10 to 20 hours.
39. The production method according to any one of claims 30 to 36, wherein the sintering atmosphere is an oxygen atmosphere.
40. A cobalt-nickel-based positive electrode material for lithium ion batteries, which is produced by the production method according to any one of claims 31 to 39.
41. A lithium ion battery comprising the positive electrode material according to any one of claims 1 to 29 or 40.
42. Use of the positive electrode material of any one of claims 1 to 29 or claim 40 or the lithium ion battery of claim 41 in a lithium electrical energy source.
43. The use according to claim 42, in mobile communication equipment, in electric vehicles.
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Address after: 550003 building 32 and 33, South Park, high end equipment manufacturing industrial park, Gui'an New District, Guiyang City, Guizhou Province Applicant after: GUIZHOU GAODIAN TECHNOLOGY Co.,Ltd. Applicant after: GAODIAN (SHENZHEN) TECHNOLOGY Co.,Ltd. Address before: 518000 Room 219, 2A Building, New Energy Industrial Park, Kanghesheng Building, No. 1 Chuangsheng Road, Xili Street, Nanshan District, Shenzhen City, Guangdong Province Applicant before: GAODIAN (SHENZHEN) TECHNOLOGY Co.,Ltd. Applicant before: GUIZHOU GAODIAN TECHNOLOGY Co.,Ltd. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |