CN114275828A - Nickel-rich material and preparation method thereof, positive plate, battery and electric equipment - Google Patents
Nickel-rich material and preparation method thereof, positive plate, battery and electric equipment Download PDFInfo
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Abstract
The invention relates to a nickel-rich material and a preparation method thereof, a positive plate, a battery and electric equipment. In the preparation method of the nickel-rich material, firstly, part of lithium salt and other metals in the preparation raw materials are used as precursor raw materials to prepare a precursor, so that elements contained in the prepared precursor are the same as elements contained in the finally prepared nickel-rich material in types, and the elements and the precursor have similar macroscopic morphological structures; and mixing the precursor with the rest lithium salt, sintering, and lithiating the precursor in the process to obtain the nickel-rich material with a more stable structure and a Karman shape coefficient phi of 0.8 or more, so that the nickel-rich material can prolong the cycle service life of a lithium ion battery when used as an anode active material for preparing the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nickel-rich material and a preparation method thereof, a positive plate, a battery and electric equipment.
Background
The lithium ion battery has many advantages of high energy density, high power density, high coulombic efficiency, environmental friendliness, no memory effect and the like, and is widely applied to the fields of electronic equipment, electric automobiles, medical electronic equipment, aerospace, power grids and the like, such as batteries of electric equipment such as automobiles, mobile phones, video cameras, digital cameras, notebook computers and the like. Therefore, lithium ion batteries increasingly occupy the main market of batteries, and have a very mature technical market particularly in the field of electronic devices. With the rapid development of science and technology, especially the development of electric automobile technology, higher requirements are also put forward on the cycle life of lithium ion batteries.
The positive active material is a decisive component of the performance of the lithium ion battery, the property of the positive active material adopted in the lithium ion battery determines the performance of the lithium ion battery to a great extent, the positive active materials which are successfully commercialized comprise lithium cobaltate, lithium manganate, lithium iron phosphate and the like, but the positive materials all have defects and defects, and the ternary positive material becomes a main positive active material for preparing the lithium ion battery due to the advantages of high discharge capacitance, excellent reaction reversibility, excellent large-current discharge capacity, wide charge-discharge voltage range, small toxicity and the like. However, the lithium ion battery made of the ternary cathode material is easy to crack in the repeated charging and discharging process, has a short cycle service life, and cannot meet the higher service life requirement of modern technologies on the lithium ion battery.
Thus, the prior art remains to be improved.
Disclosure of Invention
Based on the above, the invention provides a nickel-rich material capable of prolonging the cycle life of a lithium ion battery, a preparation method thereof, a positive plate, a battery and electrical equipment.
In one aspect of the invention, a method for preparing a nickel-rich material is provided, which comprises the following steps:
providing preparation raw materials according to the stoichiometric ratio of the chemical formula shown in the formula (1), wherein the preparation raw materials comprise lithium salt and other metal salts except the lithium salt;
Li(1+a1)NixCoyM(1-x-y)O2 (1)，
wherein a1 is more than or equal to 0.03 and less than or equal to 0.1, x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, 0 is more than or equal to 1-x-y and less than or equal to 0.40, and M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V, Cu and Zr.
Preparing a nickel-rich precursor by using the other metal salts and a part of the lithium salt as precursor raw materials;
and mixing the nickel-rich precursor with the rest lithium salt, and sintering to obtain the nickel-rich material.
In some embodiments, the sintering step is performed in an oxygen-containing atmosphere, the sintering temperature is 600-700 ℃, and the sintering time is 5-10 h.
In some of these embodiments, the nickel-rich precursor has a karman shape factor ψ greater than 0.7 and a BET less than 0.5 square meters per gram.
In some embodiments, the stoichiometric ratio of the elements in the precursor raw material is as shown in formula (2):
LicNixCoyM(1-x-y)O2 (2)，
wherein c is more than 0 and less than 1;
the ratio of the number of moles of Li element in the remaining lithium salt to the total number of moles of Ni element, Co element and M element in the other metal salt is (1+ a 1-c): 1.
in some of these embodiments, the nickel-rich material has the formula Li(1+a2)NixCoyM(1-x-y)O(2-b)；-0.10≤a2≤0.20。
In some of these embodiments, the lithium salt is selected from at least one of lithium hydroxide, lithium nitrate, lithium carbonate, lithium sulfate, and lithium acetate.
In some of these embodiments, the other metal salts include nickel salts, cobalt salts, and M-containing salts; the nickel salt is selected from at least one of nickel hydroxide, nickel carbonate, nickel sulfate and nickel acetate; and/or
The cobalt salt is at least one selected from cobalt hydroxide, cobalt carbonate, cobalt sulfate and cobalt acetate; and/or
The M-containing salt is selected from at least one of M-containing hydroxide, M-containing sulfate, M-containing carbonate and M-containing acetate.
In another aspect of the invention, a nickel-rich material is provided, which is prepared by the preparation method of the nickel-rich material.
In still another aspect of the present invention, there is provided a positive electrode sheet comprising a current collector and an active layer formed on the current collector, the composition of the active layer comprising the nickel-rich material as described above.
In still another aspect of the present invention, there is provided a battery including the positive electrode tab as described above.
In yet another aspect of the present invention, a powered device is provided, which comprises a battery as described above.
In the preparation method of the nickel-rich material, part of lithium salt and other metal salt in the preparation raw materials are used as precursor raw materials, and the nickel-rich precursor is prepared, so that elements contained in the prepared nickel-rich precursor are the same as elements contained in the finally prepared nickel-rich material in types, and the elements and the finally prepared nickel-rich material have similar macroscopic morphological structures; and then mixing and sintering the nickel-rich precursor with the rest lithium salt, and further lithiating the nickel-rich precursor in the process, so that the prepared nickel-rich material has a more stable structure and a specific morphology, the Karman shape coefficient phi of the nickel-rich material can reach 0.8 or above, and the cycle service life of the lithium ion battery can be prolonged when the prepared nickel-rich material is used as an anode active material to prepare the lithium ion battery.
Further, in the preparation method, the sintering step is carried out in an oxygen-containing atmosphere, the sintering temperature is 600-700 ℃, and the sintering time is 5-10 h.
The nickel-rich material prepared by the preparation method of the nickel-rich material has a stable structure, the Karman shape coefficient psi can reach 0.8 and above, and the cycle service life of the lithium ion battery can be prolonged.
Drawings
FIG. 1 is an XRD pattern of a nickel-rich precursor and a nickel-rich material prepared in example 1;
FIG. 2 is an electron micrograph of a nickel-rich precursor prepared in example 1;
FIG. 3 is an XRD pattern of the precursor and the nickel-rich material prepared in comparative example 1;
FIG. 4 is an electron micrograph of the precursor prepared in example 1;
FIG. 5 is a graph of cycle life testing of nickel-rich materials made in example 1 and comparative example 1;
FIG. 6 is an SEM image of the nickel-rich materials obtained in example 1(A) and comparative example 1(B) after cycle testing.
Detailed Description
In order that the invention may be more fully understood, preferred embodiments of the invention are now described. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The traditional method for preparing the ternary cathode material comprises the following steps: firstly, preparing a precursor containing the ternary main body material but not containing lithium, further sintering the precursor and a lithium source, and lithiating the precursor to obtain the ternary cathode material. In order to improve the stability of the ternary cathode material and further provide the cycle performance of the prepared lithium ion battery, technicians often adopt a precipitation method to prepare a precursor which contains the ternary main material and does not contain lithium and is provided with a coating layer, so that the stability of the ternary cathode material is improved, but the requirement of modern science and technology on the higher service life of the lithium ion battery is still difficult to meet.
The skilled person in the present invention finds in the study: the karman shape coefficient psi of the ternary cathode material has great influence on the stability of the ternary cathode material, and further researches on the traditional technology show that: the karman shape coefficient psi of the ternary cathode material prepared by the traditional technology is less than 0.8, and when the ternary cathode material is applied to a lithium ion battery, cracks are easy to occur in the repeated charging and discharging process, so that the battery is subjected to thermal runaway and is ignited and exploded.
Based on the above, after a lot of experiments, technicians of the invention obtain the nickel-rich material capable of prolonging the cycle life of the lithium battery and the preparation method thereof. The details are as follows.
One embodiment of the present invention provides a method for preparing a nickel-rich material, including the following steps S10 to S30.
Step S10, providing preparation raw materials according to the stoichiometric ratio of the chemical formula shown in the formula (1), wherein the preparation raw materials comprise lithium salt and other metal salts except the lithium salt;
Li(1+a1)NixCoyM(1-x-y)O2 (1)，
wherein a1 is more than or equal to 0.03 and less than or equal to 0.1, x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, 0 is more than or equal to 1-x-y and less than or equal to 0.40, and M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V, Cu and Zr.
And step S20, preparing a nickel-rich precursor by using other metal salts and a part of lithium salt as precursor raw materials.
And step S30, mixing the nickel-rich precursor with the rest lithium salt, and sintering to obtain the nickel-rich material.
In the preparation method of the nickel-rich material, part of lithium salt and other metal salt in the preparation raw materials are used as precursor raw materials to prepare a nickel-rich precursor, so that elements contained in the prepared nickel-rich precursor are the same as elements contained in the finally prepared nickel-rich material in types, and the elements and the finally prepared nickel-rich material have similar macroscopic morphological structures; and then mixing and sintering the nickel-rich precursor with the rest lithium salt in the preparation raw material, and further lithiating the nickel-rich precursor in the process, so that the prepared nickel-rich material has a more stable structure and a specific morphology, the Karman shape coefficient phi of the nickel-rich material can reach 0.8 or above, and when the prepared nickel-rich material is used as an anode active material to prepare a lithium ion battery, the cycle service life of the lithium ion battery can be prolonged.
The technical personnel of the invention discover in the research of the traditional preparation method of the ternary cathode material that: on one hand, the karman shape coefficient psi of the precursor containing the ternary main body material but not containing lithium prepared by some technologies in the traditional preparation method is larger than 0.7, but because the structure of the precursor is far from the framework of the final ternary cathode material, higher energy is needed in the subsequent sintering lithiation process, higher sintering temperature and longer sintering time need to be controlled, and meanwhile, in order to avoid the volatilization of lithium at high temperature for a long time, more lithium salt needs to be added, so that the energy consumption is increased, and the raw material cost is also increased; on the other hand, some of the conventional preparation methods have a karman shape coefficient psi of a precursor containing a ternary host material but not containing lithium, which is less than 0.7, but in order to ensure that a lithium salt can rapidly permeate into the precursor in the subsequent lithiation process and reduce volatilization, the high porosity characteristic of a porous structure needs to be maintained, and the subsequent sintering needs to be performed at a higher temperature. Thus, the finished product prepared by the traditional technology has low Karman coefficient, consumes more energy and has high cost.
In some of these embodiments, the nickel-rich precursor has a karman shape factor ψ of greater than 0.7 and a BET of less than 0.5 square meters per gram.
The Karman shape factor psi of the precursor is greater than 0.7 and less than 8; 0< BET < 0.5.
BET, i.e., refers to the specific surface area.
In some embodiments, the sintering step is performed in an oxygen-containing atmosphere, the sintering temperature is 600-700 ℃, and the sintering time is 5-10 h.
In the invention, because the elements contained in the nickel-rich precursor prepared firstly and the elements contained in the nickel-rich material prepared finally have the same types and the same macroscopic morphological structures, the nickel-rich precursor is further lithiated in the subsequent sintering process, the required energy is lower in the process, and the nickel-rich material with a stable structure can be obtained at a milder sintering temperature and in a shorter sintering time.
In some embodiments, the stoichiometric ratio of the elements in the precursor material is as shown in formula (2):
LicNixCoyM(1-x-y)O2 (2)，
wherein c is more than 0 and less than 1;
the ratio of the number of moles of Li element in the remaining lithium salt to the total number of moles of Ni element, Co element and M element in the other metal salt is (1+ a 1-c): 1.
preferably, 0< c < 0.65.
Further, the molecular formula of the nickel-rich precursor is Lic1NixCoyM(1-x-y)Od，0＜c＜1，0＜d≤2.1。
It should be noted that, during the preparation process of the nickel-rich precursor, the lithium salt may volatilize, so the composition ratio of the prepared nickel-rich precursor and the ratio of the precursor raw material may vary, wherein c1 may be the same as or different from the value of c, and accordingly, the ratio of oxygen may also vary.
In some of these embodiments, the nickel-rich material has the formula Li(1+a2)NixCoyM(1-x-y)O(2-b)；-0.10≤a2≤0.20，-0.05≤b≤0.10。
It should be noted that, during the sintering process, the lithium salt may volatilize slightly, so the composition ratio of the prepared nickel-rich material has a slight difference from theory.
Further, the molecular formula of the nickel-rich material is Li1NixCoyM(1-x-y)O2。
It is understood that the above lithium salt may be a lithium salt commonly used in the art, i.e., a lithium salt containing no chlorine and nitrogen.
In some of these embodiments, the lithium salt is selected from at least one of lithium hydroxide, lithium carbonate, lithium sulfate, and lithium acetate.
In some of these embodiments, the other metal salts include nickel salts, cobalt salts, and salts containing M.
In some of these embodiments, the nickel salt is selected from at least one of nickel hydroxide, nickel carbonate, nickel sulfate, and nickel acetate.
In some of these embodiments, the cobalt salt is selected from at least one of cobalt hydroxide, cobalt carbonate, cobalt sulfate, and cobalt acetate.
In some of these embodiments, the M-containing salt is selected from at least one of a M-containing hydroxide, a M-containing sulfate, a M-containing carbonate, and a M-containing acetate.
It is noted that M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V, Cu and Zr, and when M is selected from a plurality of metals thereof, the types of salts of the different metals may be the same or different, and are independently selected from at least one of hydroxides, sulfates, carbonates and acetates thereof.
In some of these embodiments, the step of preparing the nickel-rich precursor employs a spray drying process or a solid phase sintering process.
In some embodiments, the step of preparing the nickel-rich precursor is a spray drying method, comprising the steps of:
mixing the precursor raw material with a solvent, and then carrying out spray drying in an oxidizing atmosphere at 1000-1200 ℃ to obtain the nickel-rich precursor.
In some of these embodiments, the step of producing the nickel-rich precursor uses a solid phase sintering process, comprising the steps of:
mixing the precursor raw material with a solvent, and then carrying out solid-phase sintering for 6-8 h at 1000-1200 ℃ in an oxidizing atmosphere.
In some of these embodiments, the solvent is at least one of ethanol and water.
The embodiment of the invention also provides a nickel-rich material which is prepared by the preparation method of the nickel-rich material.
The nickel-rich material has stable structure, the Karman shape coefficient psi can reach 0.8 and above, and the cycle service life of the lithium ion battery can be prolonged.
An embodiment of the present invention further provides a positive electrode sheet including a current collector and an active layer formed on the current collector, wherein the active layer includes the nickel-rich material as described above.
The nickel-rich material has a stable structure, the Karman shape coefficient phi can reach 0.8 or above, and the positive plate prepared from the nickel-rich material can prolong the cycle service life of the lithium ion battery.
In some embodiments, the composition of the active layer of the positive electrode sheet further includes a binder and a conductive agent.
The binder and the conductive agent may be selected from binders and conductive agents for electrodes, which are generally used in the art.
In some embodiments, the conductive agent in the positive electrode sheet is selected from at least one of graphite, carbon nanotubes, nanofibers, carbon black, and graphene.
Specifically, the material can be selected from SP and KS-6, the negative electrode is at least one of graphite conductive carbon black Super-P Li, Ketjen black ECP with a branched chain structure, SFG-6, vapor grown carbon fiber VGCF, carbon nano tube CNTs, graphene and a composite conductive agent thereof.
In some embodiments, the binder comprises at least one of polyvinyl alcohol, polytetrafluoroethylene, and polyvinylidene fluoride.
In some embodiments, the current collector is made of a metal foil; further, the current collector is made of gold foil or aluminum foil.
An embodiment of the invention also provides a battery, which comprises the positive plate.
The battery provided by the invention contains the positive plate, the components of the positive plate comprise the nickel-rich material, and the nickel-rich material can be kept stable in the charging and discharging processes of the battery, so that the cycling stability of the battery is improved, and the cycling service life of the battery is longer.
In some of these embodiments, the battery is a lithium ion battery.
In some of these embodiments, the battery further comprises a negative electrode sheet and an electrolyte. Further, if the electrolyte is a liquid electrolyte, the battery further comprises a separator.
In particular, the separator is selected from a Polyethylene (PE) separator or a polypropylene (PP).
In some embodiments, the negative active material in the negative electrode sheet includes graphite, mesophase micro carbon spheres, hard carbon, soft carbon, elemental silicon, silicon-oxygen compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2TiO of spinel structure2-Li4Ti5O12And a Li-Al alloy.
The graphite may be natural graphite or synthetic graphite.
In some embodiments, the conductive agent in the negative electrode sheet is at least one selected from graphite, carbon nanotubes, nanofibers, carbon black, and graphene.
Specifically, the conductive agent in the negative plate can be selected from SP and KS-6, the negative electrode is at least one of graphite conductive carbon black Super-P Li, Keqin black ECP with a branched chain structure, SFG-6, vapor grown carbon fiber VGCF, carbon nano tube CNTs, graphene and a composite conductive agent thereof.
In some of these embodiments, the electrolyte is selected from the group consisting of electrolytic lithium salts, such as lithium bistrifluoromethylsulfonate imide LiTFSI, lithium hexafluorophosphate.
An embodiment of the present invention further provides an electric device, which includes the battery as described above.
The electric equipment comprises the battery and has long service life.
The electric equipment is electric equipment, including but not limited to: automobiles, air conditioners, humidifiers, telephones, recorders, range hoods, microwave ovens, washing machines, cell phones, cell phone chargers, computers, fans, printers, and the like.
In some embodiments, the electric device is an automobile.
The battery has high cycling stability and long service life, and can be used for preparing automobiles, further improve the cruising ability of the automobiles and promote the development of the field of electric automobiles.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
The following are specific examples.
Example 1
(1) Synthesizing a nickel-rich precursor: nickel acetate, cobalt acetate, manganese acetate and lithium acetate are mixed according to the chemical formula Li0.35Ni0.88Co0.05Mn0.07O2Mixing the components in proportion, dissolving the mixture in ethanol to obtain a mixed solution with the concentration of 2mol/L, adjusting the temperature of spray pyrolysis equipment to 1100 ℃, and performing spray drying on the mixed solution by taking oxygen with the flow of 3mol/L as carrier gas to obtain a nickel-rich precursor. Tests show that the molecular formula of the nickel-rich precursor is Li0.33Ni0.88Co0.05Mn0.07O1.2The karman shape factor ψ is 0.76 and BET is 0.36 m/g.
XRD test is carried out on the prepared nickel-rich precursor, XRD test curve is shown as (a) in attached figure 1, and the nickel-rich precursor has alpha-NaFeO2A layer-shaped structure; further, the prepared nickel-rich precursor is placed under an electron microscope, and the electron microscope image is shown in the attached figure 2.
(2) Mixing the nickel-rich precursor with lithium hydroxide, wherein the ratio of the mole number of Li elements in the lithium hydroxide to the sum of the mole numbers of Ni elements, Co elements and Mn elements in the nickel-rich precursor is 0.69: 1, then placing the material in a sintering furnace to sinter for 6 hours at 650 ℃ in pure oxygen atmosphere to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: LiNi0.88Co0.05Mn0.07O2The karman shape factor ψ is 0.89.
Wherein, the raw materials used in the whole process of preparing the nickel-rich material accord with the chemical formula Li(1+0.04)Ni0.88Co0.05M0.07O2。
Carrying out X on the prepared nickel-rich materialThe RD test and XRD test curve are shown as (b) in the attached figure 1, and the result shows that: the prepared nickel-rich material also has alpha-NaFeO2And (3) forming a layer structure, wherein the layer structure has a similar structure with the nickel-rich precursor prepared in the step (1).
(3) Mixing the nickel-rich cathode material prepared in the step (2) with carbon black and polyvinylidene fluoride powder according to a ratio of 96: 2: 2, adding an NMP solvent, uniformly stirring to obtain anode slurry, and coating the anode slurry on an aluminum foil with the thickness of 14 microns to obtain the anode plate.
Coating artificial graphite on 8-micron copper foil to prepare a negative plate, taking a carbonate solution containing 1.5mol/L lithium hexafluorophosphate as an electrolyte, and then assembling the negative plate, the positive plate, a PP diaphragm with the thickness of 12 microns and the electrolyte to prepare the lithium ion battery. Through the test: when the lithium ion battery is charged and discharged at the voltage range of 3.0V-4.2V and the multiplying power of 0.33C under the temperature of 30 ℃, the first-circle capacity is 1 Ah.
(4) And (2) placing the lithium ion battery in a constant-temperature oven at 30 ℃, repeatedly charging and discharging at 1C rate for 2000 times within the voltage range of 3.0-4.2V, then discharging the battery to 2.8V at 0.33C rate, then disassembling the battery, taking out a positive pole piece, and observing the cracking condition of the positive pole material.
The results show that: after the lithium ion battery is repeatedly charged and discharged for 2000 times, the positive electrode material in the prepared lithium ion battery still keeps complete structure and does not crack.
Example 2
(1) Synthesizing a nickel-rich precursor: nickel hydroxide, cobalt hydroxide, manganese hydroxide and lithium acetate are mixed according to the chemical formula Li0.42Ni0.88Co0.05Mn0.07O2Mixing at a certain ratio, placing in pure alumina ceramic bowl at a ratio of 100kg/cm2The mixture layer is pressed until the thickness of the mixture layer is 3cm, then the mixture layer is placed in a sintering furnace at the temperature of 1100 ℃, oxygen is introduced into the sintering furnace at the flow rate of 5mol/L, and sintering is carried out for 6 hours, so as to obtain the nickel-rich precursor. Tests show that the molecular formula of the nickel-rich precursor is Li0.4Ni0.88Co0.05Mn0.07O1.2The karman shape factor ψ is 0.74 and BET is 0.34 m/g.
(2) Will be at the topMixing the nickel-rich precursor with lithium hydroxide, wherein the ratio of the mole number of Li element in the lithium hydroxide to the sum of the mole numbers of Ni element, Co element and Mn element in the nickel-rich precursor is 0.64: 1, then placing the material in a sintering furnace, introducing oxygen into the sintering furnace at the flow rate of 10mol/L, sintering the material for 8 hours at the temperature of 700 ℃ to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: LiNi0.88Co0.05Mn0.07O2The karman form factor ψ is 0.86.
Wherein, the raw materials used in the whole process of preparing the nickel-rich material accord with the chemical formula Li(1+0.06)Ni0.88Co0.05M0.07O2。
XRD tests are respectively carried out on the prepared nickel-rich precursor and the nickel-rich material, and the results show that: the prepared nickel-rich precursor and the nickel-rich material have similar structures.
(3) Mixing the nickel-rich cathode material prepared in the step (2) with carbon black and pvdf powder according to a ratio of 96: 2: 2, adding an NMP solvent, uniformly stirring to obtain anode slurry, and coating the anode slurry on an aluminum foil with the thickness of 14 microns to obtain an anode plate.
Coating artificial graphite on 8 micron copper foil to prepare a negative plate, taking a carbonate solution containing 1.5mol/L lithium hexafluorophosphate as an electrolyte, then assembling the negative plate, the positive plate, a PP diaphragm with the thickness of 12 microns and the electrolyte to prepare a lithium ion battery, and testing: when the lithium ion battery is charged and discharged at the voltage range of 3.0V-4.2V and the multiplying power of 0.33C under the temperature of 30 ℃, the first-circle capacity is 1 Ah.
(4) And (2) placing the lithium ion battery in a constant-temperature oven at 30 ℃, repeatedly charging and discharging at 1C rate for 2000 times within the voltage range of 3.0-4.2V, then discharging the battery to 2.8V at 0.33C rate, then disassembling the battery, taking out a positive pole piece, and observing the cracking condition of the positive pole material.
The results show that: after the charge and discharge were repeated 2000 times, the positive electrode material in the lithium ion battery was observed under an electron microscope, as shown in fig. 6 (a), the positive electrode material still maintained structural integrity and did not crack.
Example 3
(1) Synthesizing a nickel-rich precursor: nickel hydroxide, cobalt hydroxide, manganese hydroxide and lithium acetate are mixed according to the chemical formula Li0.64Ni0.88Co0.05Mn0.07O2Mixing at a certain ratio, placing in pure alumina ceramic bowl at a ratio of 100kg/cm2The mixture layer is pressed until the thickness of the mixture layer is 3cm, then the mixture layer is placed in a sintering furnace at the temperature of 1100 ℃, oxygen is introduced into the sintering furnace at the flow rate of 5mol/L, and sintering is carried out for 6 hours, so as to obtain the nickel-rich precursor. Tests show that the molecular formula of the nickel-rich precursor is Li0.62Ni0.88Co0.05Mn0.07O1.2The karman shape factor ψ is 0.79 and BET is 0.3 m/g.
(2) Mixing the nickel-rich precursor with lithium hydroxide, wherein the ratio of the mole number of Li elements in the lithium hydroxide to the sum of the mole numbers of Ni elements, Co elements and Mn elements in the nickel-rich precursor is 0.41: 1:1, then placing the material in a sintering furnace, introducing oxygen into the sintering furnace at the flow rate of 10mol/L, sintering the material for 8 hours at the temperature of 700 ℃ to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: LiNi0.88Co0.05Mn0.07O2The karman shape factor ψ is 0.85.
Wherein, the raw materials used in the whole process of preparing the nickel-rich material accord with the chemical formula Li(1+0.05)Ni0.88Co0.05M0.07O2。
XRD tests are respectively carried out on the prepared nickel-rich precursor and the nickel-rich material, and the results show that: the prepared nickel-rich precursor and the nickel-rich material have similar structures.
Subsequent steps (3) to (4): same as in steps (3) to (4) of example 1.
The results show that: after the lithium ion battery is repeatedly charged and discharged for 2000 times, the positive electrode material in the prepared lithium ion battery still keeps complete structure and does not crack.
Example 4
Example 4 is essentially the same as example 1, except that: in the step (1), the manganese acetate is replaced by the copper acetate with the same mole number.
The rest of the procedure was the same as in example 1.
The results show that: the molecular formula of the prepared nickel-rich material is as follows: LiNi0.88Co0.05Cu0.07O2The karman shape coefficient psi is 0.86, the prepared nickel-rich material and the prepared nickel-rich precursor have similar structures, and the positive electrode material of the prepared lithium ion battery still keeps complete structure and does not crack after being repeatedly charged and discharged for 2000 times.
Example 5
Example 5 is essentially the same as example 1, except that: in the step (1), the manganese acetate is replaced by the titanium acetate with the same mole number.
The rest of the procedure was the same as in example 1.
The results show that: the molecular formula of the prepared nickel-rich material is as follows: LiNi0.88Co0.05Ti0.07O2The karman shape coefficient psi is 0.84, the prepared nickel-rich material and the prepared nickel-rich precursor have similar structures, and the positive electrode material of the prepared lithium ion battery still keeps complete structure and does not crack after being repeatedly charged and discharged for 2000 times.
Example 6
Example 6 is essentially the same as example 1, except that: in the step (1), the manganese acetate is replaced by magnesium acetate with the same mole number.
The rest of the procedure was the same as in example 1.
The results show that: the molecular formula of the prepared nickel-rich material is as follows: LiNi0.88Co0.05Mg 0.07O2The karman shape coefficient psi is 0.87, the prepared nickel-rich material and the prepared nickel-rich precursor have similar structures, and the positive plate of the prepared lithium ion battery still keeps complete structure and does not crack after being repeatedly charged and discharged for 2000 times.
Comparative example 1
(1) Synthesizing a nickel-rich precursor: nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the chemical formula Ni0.88Co0.05Mn0.07(OH)2Proportionally mixing, dissolving in deionized water to obtain a mixed solution with the concentration of 2mol/L, adding the mixed solution with 2mol/L NaOH aqueous solution and 5mol/L ammonia aqueous solution into a reaction kettle with a stirring device at the same time, and stirring under the protection of nitrogen for 60 minutesAnd (3) carrying out precipitation reaction at the temperature of DEG C, wherein NaOH is used as a precipitator, ammonia water is used as a complexing agent, the reaction is stopped when the particle size D50 of the precursor is 5 mu m, filtering is carried out, and the filter cake is dried in vacuum at the temperature of 100 ℃ to obtain the precursor. The molecular formula of the precursor is Ni through testing0.88Co0.05Mn0.07(OH)2The karman shape factor ψ is 0.45 and BET is 11.03 m/g.
(2) Mixing the precursor with lithium hydroxide, wherein the ratio of the mole number of Li element in the lithium hydroxide to the sum of the mole numbers of Ni element, Co element and Mn element in the nickel-rich precursor is 1.04: 1, then placing the material in a sintering furnace to sinter the material for 18 hours at 750 ℃ in a pure oxygen atmosphere to obtain a nickel-rich material, and testing: the molecular formula of the nickel-rich material is as follows: LiNi0.88Co0.05Mn0.07O2The karman shape factor ψ is 0.6.
XRD tests are respectively carried out on the prepared precursor and the nickel-rich material, the XRD test curve of the precursor is shown as (a) in the attached figure 3, the XRD test curve of the nickel-rich material is shown as (b) in the attached figure 3, and the results show that: the structure of the prepared nickel-rich material is far from that of the precursor prepared in the step (1). Further, the prepared precursor was placed under an electron microscope, and the electron microscope image is shown in fig. 4.
Comparing fig. 2 and fig. 4, it can be seen that the nickel-rich precursor prepared in example 1 is far from the precursor prepared in comparative example 1 in morphology.
Subsequent steps (3) to (4) were the same as in steps (3) to (4) of example 1.
The results show that: during the cycle test, the capacity retention rate of the battery prepared by using the nickel-rich material prepared in the comparative example 1 is greatly attenuated along with the increase of the cycle life times, and the capacity retention rate of the battery prepared by using the nickel-rich material prepared in the example 1 is reduced along with the increase of the cycle life times by a much smaller extent than that of the comparative example 1.
After the cycle test for 2000 times, the positive electrode material in the lithium ion battery prepared in comparative example 1 was observed under an electron microscope, and as shown in fig. 6 (B), the positive electrode material cracked and a significant crack appeared.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. The preparation method of the nickel-rich material is characterized by comprising the following steps of:
providing preparation raw materials according to the stoichiometric ratio of the chemical formula shown in the formula (1), wherein the preparation raw materials comprise lithium salt and other metal salts except the lithium salt;
Li(1+a1)NixCoyM(1-x-y)O2 (1)，
wherein a1 is more than or equal to 0.03 and less than or equal to 0.1, x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.1, 0 is more than or equal to 1-x-y and less than or equal to 0.40, and M is at least one of Mn, Al, Ti, Ba, Sr, Mg, Cr, Zn, V, Cu and Zr;
preparing a nickel-rich precursor by using the other metal salts and a part of the lithium salt as precursor raw materials;
and mixing the nickel-rich precursor with the rest lithium salt, and sintering to obtain the nickel-rich material.
2. The method of claim 1, wherein the sintering step is performed in an oxygen-containing atmosphere at a temperature of 600 ℃ to 700 ℃ for a time of 5h to 10 h.
3. The method of claim 2, wherein the nickel-rich precursor has a karman shape factor ψ greater than 0.7 and a BET less than 0.5 m/g.
4. The method for preparing the nickel-rich material according to any one of claims 1 to 3, wherein the stoichiometric ratio of each element in the precursor raw material is as shown in formula (2):
LicNixCoyM(1-x-y)O2 (2)，
wherein c is more than 0 and less than 1;
the ratio of the number of moles of Li element in the remaining lithium salt to the total number of moles of Ni element, Co element and M element in the other metal salt is (1+ a 1-c): 1.
5. the method for preparing the nickel-rich material according to any one of claims 1 to 3, wherein the molecular formula of the nickel-rich material is Li(1+a2)NixCoyM(1-x-y)O(2-b)；-0.10≤a2≤0.20，-0.05≤b≤0.10。
6. The method of any of claims 1-3, wherein the lithium salt is selected from at least one of lithium hydroxide, lithium carbonate, lithium sulfate, and lithium acetate.
7. A method of producing a nickel-rich material as claimed in any one of claims 1 to 3, wherein the other metal salts include nickel salts, cobalt salts and M-containing salts; the nickel salt is selected from at least one of nickel hydroxide, nickel carbonate, nickel sulfate and nickel acetate; and/or
The cobalt salt is at least one selected from cobalt hydroxide, cobalt carbonate, cobalt sulfate and cobalt acetate; and/or
The M-containing salt is selected from at least one of M-containing hydroxide, M-containing sulfate, M-containing carbonate and M-containing acetate.
8. A nickel-rich material prepared by the method for preparing the nickel-rich material according to any one of claims 1 to 7.
9. A positive electrode sheet comprising a current collector and an active layer formed on the current collector, the composition of the active layer comprising the nickel-rich material according to claim 8.
10. A battery comprising the positive electrode sheet according to claim 9.
11. An electrical consumer, characterized in that the consumer comprises a battery according to claim 10.
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