CN115286048A - Positive electrode material precursor and preparation method and application thereof - Google Patents

Positive electrode material precursor and preparation method and application thereof Download PDF

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CN115286048A
CN115286048A CN202210878622.9A CN202210878622A CN115286048A CN 115286048 A CN115286048 A CN 115286048A CN 202210878622 A CN202210878622 A CN 202210878622A CN 115286048 A CN115286048 A CN 115286048A
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positive electrode
electrode material
precursor
equal
comparative example
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汪乾
阮丁山
李长东
刘伟健
刘更好
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202210878622.9A priority Critical patent/CN115286048A/en
Priority to PCT/CN2022/118001 priority patent/WO2024021243A1/en
Publication of CN115286048A publication Critical patent/CN115286048A/en
Priority to FR2307958A priority patent/FR3138247A1/en
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Abstract

The invention discloses a precursor of a positive electrode material, a preparation method and application thereof, and the precursor of the positive electrode material provided by the invention comprises substances shown in the following chemical formula: ni x Co y Mn z Fe a (OH) 2 (ii) a Wherein 0<x＜1；0≤y≤0.9；0≤z≤0.9；0<a is less than or equal to 0.005; x + y + z + a =1. The precursor of the positive electrode materialThe prepared anode material has excellent cycle performance, gram specific capacity and rate capability. The invention also provides a preparation method and application of the precursor of the cathode material.

Description

Positive electrode material precursor and preparation method and application thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a precursor of a positive electrode material, and a preparation method and application thereof.
Background
In order to improve the environmental protection performance, the traditional fuel vehicles are gradually sold in a limited way, and new energy vehicles gradually enter the market. However, the new energy automobile in the current market still has the following defects: the driving range is short (range anxiety), the service life is short, hidden danger exists in safety, and related supporting facilities are not completely built.
Among them, the endurance mileage is one of the major concerns of consumers, and new energy vehicles with endurance journey exceeding 1000 km are urgently needed to be researched and developed. The endurance mileage of the new energy automobile is mainly limited by the energy density of the anode material, and the energy density is in direct proportion to the specific capacity of the material. Therefore, the method for improving the specific capacity of the cathode material to the maximum extent is the most direct and effective way for improving the energy density of the battery pack.
In addition, the service life is also one of the concerns of consumers, and the service life of the new energy automobile is limited to a certain extent by the cycle life of the cathode material, so that it is also very important to improve the cycle performance of the cathode material.
At present, methods for improving the specific capacity and the cycle performance of the anode material mainly comprise doping, cladding, special design of the structure of the anode material and the like, but the obtained effect is not ideal. Since the performance of the cathode material greatly depends on the precursor, designing a precursor with reasonable components to improve the cycle performance and the specific capacity of the cathode material is an effective way.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a precursor of the cathode material, and the prepared cathode material has excellent cycle performance and gram specific capacity.
The invention also provides a preparation method of the precursor of the cathode material.
The invention also provides application of the precursor of the cathode material.
According to an embodiment of the first aspect of the present invention, a cathode material precursor is provided, which includes a substance represented by the following chemical formula:
Ni x Co y Mn z Fe a (OH) 2 ；
wherein 0<x is less than 1; y is more than or equal to 0 and less than or equal to 0.9; z is more than or equal to 0 and less than or equal to 0.9;0<a is not more than 0.005; x + y + z + a =1.
The positive electrode material precursor provided by the embodiment of the invention has at least the following beneficial effects:
(1) In industry, the precursor of the positive electrode material is usually synthesized by coprecipitation method by using transition metal sulfate as raw material, and the obtained material usually contains SO 4 2- The impurity sulfur exists in the form of sulfur, the impurity sulfur is occluded in the impurity sulfur or adsorbed on the surface of the impurity sulfur, after the anode material precursor is prepared into the anode material, the impurity sulfur inherits the impurity sulfur in the anode material precursor, and the impurity sulfur influences the cycle performance and the gram specific capacity of the anode material, wherein the influence of sulfur is most obvious. Therefore, the electrochemical performance of the cathode material is improved to a certain extent by reducing the content of sulfur impurities in the precursor of the cathode material.
Impurities in the Bao Cangzai positive electrode material precursor are difficult to remove through later alkali washing and water washing processes; according to the invention, fe is doped in the precursor of the anode material, and because Fe, ni, co and Mn are in the same period and have similar atomic coefficients and ionic radii, the precursor can better occupy the position of transition metal in crystal lattices, thereby realizing the doping at an atomic level. Therefore, fe (iron ion) directly occupies the position of the transition metal ion (and the equilibrium electrical property with oxygen in the crystal lattice) rather than at the gap between layers, and does not need to adsorb SO 4 2- And anions such as OH & lt- & gt are used for maintaining electric neutrality, and compared with doping of other types, the Fe can be doped to reduce the adsorption of the precursor of the positive electrode material on sulfate radicals to a certain extent, so that the sulfur impurity content of the precursor of the positive electrode material is reduced.
(2) The invention provides a precursor of a positive electrode materialAfter the lithium is prepared into the anode material by sintering, fe and other transition metal ions are oxidized, wherein Fe 3+ (t 5 2g e g 0 ) And Co 3+ (t 6 2g e g 0 ) Having a similar electronic configuration, can be obtained by reducing the interlaminar linearity of Ni 2+ -O 2- -Fe 3+ The super exchange effect can reduce the Ni/Li mixed discharge in the obtained cathode material better and exert the effect of Co 3+ Similar effects. The price of Fe is superior to that of Co, and the source of Fe is wider, so that the economy of the precursor of the cathode material and the cathode material can be improved by replacing Co with partial Fe.
In addition, the phase transition of the positive electrode material is associated with the migration of transition metal ions from octahedral to tetrahedral gaps, while Fe in a high spin state 3+ Easily occupy tetrahedral gaps, thereby blocking migration paths of transition metal particles from the octahedral gaps to the tetrahedral gaps and inhibiting phase change during the cycle of the positive electrode material.
That is to say, on one hand, fe doping can play a role similar to Co to reduce cation mixed discharge in the positive electrode material, and the role is superior to that of Co; on the other hand, the transition metal ion migration can be blocked, so that the phase change of the material in the circulating process is inhibited, and the positive electrode material is endowed with good electrochemical performance, particularly circulating performance.
(3) Although the Fe doping has many advantages, if the Fe content exceeds the range required by the present invention, magnetic foreign matter is introduced, and the precursor of the positive electrode material is prepared into the positive electrode material, and further prepared into the secondary battery, the safety problems of the secondary battery, such as short circuit, self-discharge, etc., are easily caused. Therefore, the content of impurity sulfur in the precursor of the cathode material is reduced by limiting the doping amount of Fe, the Li/Ni mixed-discharge content of the cathode material prepared from the precursor of the cathode material is inhibited, and the introduction of magnetic foreign matters is avoided.
According to some embodiments of the invention, ni x Co y Mn z Fe a (OH) 2 In this case, 0.001. Ltoreq. A.ltoreq.0.005, it being understood that a may be 0.001, 0.002, 0.003, 0.004, and 0.005.
According to some embodiments of the invention, the D50 particle size of the positive electrode material precursor is between 9.5 and 10.5 μm.
According to some embodiments of the invention, the impurity sulfur content in the positive electrode material precursor is 1400ppm or less.
The content of the impurity sulfur is related to the composition of the precursor of the cathode material, particularly the nickel content, and under the same preparation condition, the content of the impurity sulfur of the precursor of the cathode material is increased along with the increase of the nickel content.
According to some embodiments of the invention, ni x Co y Mn z Fe a (OH) 2 When x is more than or equal to 0.68 and less than or equal to 0.72,0.0025 and less than or equal to 0.0035, the content of impurity sulfur in the precursor of the positive electrode material is less than or equal to 500ppm.
According to some embodiments of the invention, ni x Co y Mn z Fe a (OH) 2 In the positive electrode material precursor, when x is more than or equal to 0.78 and less than or equal to 0.82,0.0005 and less than or equal to 0.0015, the content of impurity sulfur in the positive electrode material precursor is less than or equal to 800ppm.
According to some embodiments of the invention, ni x Co y Mn z Fe a (OH) 2 When x is more than or equal to 0.90 and less than or equal to 0.92,0.0015 and less than or equal to 0.0025, the content of impurity sulfur in the precursor of the positive electrode material is less than or equal to 1400ppm.
According to some embodiments of the invention, ni x Co y Mn z Fe a (OH) 2 When x is more than or equal to 0.62 and less than or equal to 0.67,0.00 and more than or equal to a and less than or equal to 0.0005, the content of impurity sulfur in the precursor of the positive electrode material is less than or equal to 450ppm.
Furthermore, compared with the precursor of the cathode material not doped with Fe, the reduction range of the impurity sulfur content in the precursor of the cathode material provided by the invention is more than or equal to 43 percent by adopting the same preparation method.
Furthermore, compared with the precursor without Fe, the reduction range of the impurity sulfur content in the precursor of the cathode material provided by the invention is 43-60%.
The content of sulfur impurities in the precursor of the cathode material is obviously reduced, so that the cathode material prepared from the precursor of the cathode material has excellent gram specific capacity and cycle performance.
According to the embodiment of the second aspect of the invention, the preparation method of the positive electrode material precursor is provided, and comprises the steps of mixing and reacting a salt solution, ammonia water and an alkali solution;
the salt solution contains nickel ions, cobalt ions, manganese ions and iron ions;
the mass ratio of the nickel ions, the cobalt ions, the manganese ions and the iron ions is x: y: z: a.
the preparation method of the precursor of the cathode material provided by the embodiment of the invention has at least the following beneficial effects:
(1) The preparation method provided by the invention is a coprecipitation method actually, iron and other transition metals (such as Ni) are coprecipitated, and uniform doping of Fe can be realized, so that the content of sulfur impurity in the obtained positive electrode material precursor is reduced, and further, the Li/Ni mixed discharge condition in the positive electrode material prepared from the positive electrode material precursor can be reduced.
(2) In the traditional process, researchers have explored the intermittent method for preparing the low-sulfur-content nickel-cobalt-manganese ternary precursor, and particularly, the method adopts a PSP (stop reaction, sedimentation, supernatant removal and reaction start) process in the crystal growth stage, and the process has narrow applicability and relatively complex process, and can only reduce the S content to 1200ppm. The process also adopts a method of water washing and alkali washing for many times to prepare the nickel-cobalt-manganese ternary precursor large particles with low sulfur content, the S content of the precursor can be controlled below 850ppm by adopting the process, but the process and the consumption of alkali liquor are increased, and the cost and the production period are increased to a certain extent.
According to the invention, the reduction of the content of the impurity sulfur in the precursor of the cathode material can be realized only by doping iron by a coprecipitation method, so that the preparation process and the preparation cost are obviously saved, and the method is simple and easy to implement and is convenient for large-scale popularization.
According to some embodiments of the invention, the nickel ions are from NiSO 4 ·6H 2 O or anhydrous NiSO 4 。
According to some embodiments of the invention, the cobalt ion is from CoSO 4 ·7H 2 O or anhydrous CoSO 4 。
According to some embodiments of the invention, the manganese ions are from MnSO 4 ·H 2 O or anhydrous MnSO 4 。
According to some embodiments of the invention, the iron ion is from FeSO 4 ·7H 2 O or anhydrous FeSO 4 。
Trace Ca, mg impurity and SO in the precursor of positive electrode material 4 2- Combined with CaSO 4 、MgSO 4 In the form of (A), wherein CaSO 4 The Mg is slightly soluble, has larger property difference with Ni, cu and Mn, is not easy to replace transition metal ions in crystal lattices, is occluded in the crystal and is difficult to remove by methods such as simple water washing and the like. With FeSO 4 Introducing Fe doping, feSO 4 Is a strong electrolyte which is easy to dissolve, fe, ni, co and Mn are in the same period, and the atomic coefficient and the ionic radius are similar, SO that the Fe-Ni-Co-Mn alloy can better occupy the position of transition metal in crystal lattice without introducing SO between layers 4 2- 、CO 3 2- The plasma maintains charge neutrality. Due to the competitive effect of Fe and other impurities, the occlusion of the impurities in the precursor of the positive electrode material is reduced, so that the content of the sulfur impurity in the precursor of the positive electrode material is reduced.
According to some embodiments of the invention, the salt solution has a concentration of 1 to 3mol/L; the concentration is the sum of the concentrations of transition metal ions and iron ions in the salt solution.
According to some preferred embodiments of the invention, the concentration of the salt solution is 1.5 to 2.5mol/L.
According to some embodiments of the present invention, the concentration of the ammonia water in the system of the mixed reaction is 0.5 to 12g/L.
According to some preferred embodiments of the present invention, the concentration of the ammonia water in the system of the mixing reaction is 0.8 to 11g/L.
According to some embodiments of the present invention, the concentration of ammonia in the system of the mixed reaction is about 4g/L.
According to some embodiments of the invention, the system of the mixed reaction has a pH of 8.5 to 12.
According to some preferred embodiments of the present invention, the pH of the system of the mixing reaction is 9 to 11.5.
According to some embodiments of the invention, the concentration of the alkali solution is 2 to 10mol/L.
According to some embodiments of the invention, the solute of the alkali solution comprises at least one of sodium hydroxide and potassium hydroxide.
According to some preferred embodiments of the invention, the solute of the alkali solution is selected from sodium hydroxide; therefore, the effects of saving cost and increasing the concentration of the alkali solution can be achieved.
According to some embodiments of the invention, the mixing reaction is carried out under stirring; preferably, the rotation speed of the stirring state is 300 to 500rpm.
According to some embodiments of the invention, the method for preparing the cathode material precursor further comprises washing a solid-liquid mixture obtained by the mixing reaction.
According to some embodiments of the invention, the washing method comprises mixing the alkaline solution and the solid-liquid mixture in sequence, separating the solid from the liquid to obtain a solid phase, and washing the solid phase with pure water. The alkali liquor can remove sulfur impurities in the precursor of the obtained anode material as far as possible, and the pure water can be washed to remove residual alkali liquor.
Further, the temperature of the alkali liquor for washing is 55-65 ℃; the concentration of the alkali liquor is about 5mol/L.
The temperature of pure water for washing is 45-55 ℃;
during the washing process, the volume ratio of the solid-liquid mixture, the alkali liquor and the pure water is 4.
According to the embodiment of the third aspect of the invention, the preparation raw material of the cathode material comprises the cathode material precursor.
Since the positive electrode material adopts all the technical solutions of the positive electrode material precursors of the above embodiments, at least all the advantages brought by the technical solutions of the above embodiments are achieved. Namely, the obtained cathode material has low content of impurity sulfur, low lithium-nickel mixing degree, and excellent gram specific capacity and cycle performance.
According to some embodiments of the invention, the raw material for preparing the positive electrode material further comprises a lithium source.
According to some embodiments of the present invention, the raw material for preparing the positive electrode material further includes at least one of a bulk dopant, a surface dopant, and a surface coating agent.
According to some embodiments of the invention, the bulk dopant comprises ZrO 2 、Y 2 O 3 、SrO、CeO 2 、La 2 O 3 And MoO 3 At least one of (1).
According to some embodiments of the invention, the surface dopant and the surface coating agent are each independently selected from WO 3 、Al 2 O 3 、Sb 2 O 3 、TiO 2 、Nb 2 O 5 、B 2 O 3 、MgCO 3 And NaF.
According to some embodiments of the invention, the positive electrode material has a chemical formula as follows:
Li 1+b Ni x Co y Mn z Fe a M c O 2 ；
wherein B is more than or equal to 0 and less than or equal to 0.2,0 and less than or equal to 0.03, M is at least two of Ni, co, mn, zr, al, mg, ti, sr, W, Y, mo, sb, nb, sn, zn, la, ce, B and F.
According to some embodiments of the invention, li 1+b Ni x Co y Mn z Fe a M c O 2 Wherein M is derived from at least one of the bulk dopant, the surface dopant and the surface capping agent.
The bulk, surface and surface dopants are used in amounts of Li 1+b Ni x Co y Mn z Fe a M c O 2 The value of c in (1) is calculated.
According to an embodiment of the fourth aspect of the invention, a method for preparing a cathode material is provided, which comprises mixing the cathode material precursor and a lithium source and then sequentially performing first sintering and second sintering.
The preparation method of the cathode material adopts all the technical schemes of the cathode material of the embodiment, so that the preparation method at least has all the beneficial effects brought by the technical schemes of the embodiment.
According to some embodiments of the present invention, the molar ratio of lithium in the lithium source to transition metal atoms in the positive electrode material precursor is (1-1.1): 1. Since the lithium source may be burned off to some extent during the sintering process, particularly during the first sintering process, the lithium/metal ratio of the resulting positive electrode material is maintained at about 1 within the above-mentioned ratio range.
According to some embodiments of the invention, the lithium source comprises LiOH and Li 2 CO 3 At least one of (1).
According to some embodiments of the invention, the mixed feedstock further comprises a bulk dopant.
According to some embodiments of the invention, the method for preparing the positive electrode material further comprises crushing the product of the first sintering.
According to some embodiments of the invention, the crushing comprises at least one of coarse crushing and fine crushing, the former using an instrument comprising at least one of a jaw crusher and a twin roll mill, and the latter using an instrument comprising at least one of a jet mill and a mechanical mill.
According to some embodiments of the present invention, the method of preparing the cathode material further comprises blending a product of the first sintering with at least one of a surface dopant and a surface coating agent between the first sintering and the second sintering.
According to some embodiments of the invention, the atmosphere of the first sintering and the second sintering is selected from at least one of dry air and oxygen, respectively.
According to some embodiments of the invention, the constant temperature of the first sintering is 700 to 1000 ℃.
According to some embodiments of the invention, the first sintering is performed at a constant temperature of 250 to 750 ℃.
According to a fifth aspect of the embodiment of the invention, a secondary battery is provided, and the preparation raw material of the secondary battery comprises the cathode material.
Because the secondary battery adopts the cathode material, compared with the traditional secondary battery, the secondary battery has longer service life and higher energy density, and when the secondary battery is used for a power battery, the anxiety of mileage can be effectively relieved, and the battery replacement period can be prolonged.
According to a sixth aspect of the embodiment of the invention, the application of the secondary battery in the fields of power batteries and energy storage is proposed.
Unless otherwise specified, "about" in the present invention means an allowable error of ± 2%, for example, about 100 actually means 100 ± 100 × 2%, i.e., 98 to 102.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is an SEM image of a precursor of a positive electrode material obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a positive electrode material obtained in example 5 of the present invention;
fig. 3 is an XRD spectrum of the cathode material obtained in example 5 of the present invention;
fig. 4 is an SEM image of the positive electrode material precursor obtained in comparative example 1 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
Example 1
This example prepared a precursor of a positive electrode material,designed chemical formula as Ni 0.70 Co 0.05 Mn 0.247 Fe 0.003 (OH) 2 (the actual preparation may have slight deviation), the specific steps are as follows:
mixing NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O、FeSO 4 ·7H 2 O is prepared into a salt solution (feeding material) with the concentration of 2mol/L according to the molar ratio of 0.70 0.70 Co 0.05 Mn 0.247 Fe 0.003 (OH) 2 And washing with 5 mol/L60 ℃ hot NaOH solution and 50 ℃ pure water for 20min and 10min respectively, wherein the volumes of the precursor slurry, alkali liquor and pure water are respectively 4.
Example 2
In this example, a precursor of a positive electrode material was prepared with a chemical formula of Ni 0.80 Co 0.1 Mn 0.099 Fe 0.001 (OH) 2 The method comprises the following specific steps:
mixing NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O、FeSO 4 ·7H 2 O is prepared into a salt solution (feeding) with the concentration of 2mol/L according to the molar ratio of 0.80 0.80 Co 0.1 Mn 0.099 Fe 0.001 (OH) 2 And washing with 5 mol/L60 ℃ hot NaOH solution and 50 ℃ pure water, wherein the washing time is 20min and 10min respectively, and the volumes of the precursor slurry, alkali liquor and pure water are respectively 4.
Example 3
In this example, a precursor of a positive electrode material with a chemical formula of Ni was prepared 0.92 Co 0.04 Mn 0.038 Fe 0.002 (OH) 2 The method comprises the following specific steps:
mixing NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O、FeSO 4 ·7H 2 O is prepared into a saline solution (feeding) with the concentration of 1.5mol/L according to the molar ratio of 0.92 0.92 Co 0.04 Mn 0.038 Fe 0.002 (OH) 2 And washing with 5 mol/L60 ℃ hot NaOH solution and 50 ℃ pure water, wherein the washing time is 20min and 10min respectively, and the volumes of the precursor slurry, alkali liquor and pure water are respectively 4.
Example 4
In this example, a precursor of a positive electrode material with a chemical formula of Ni was prepared 0.65 Co 0.12 Mn 0.225 Fe 0.005 (OH) 2 The method comprises the following specific steps:
mixing NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O、FeSO 4 ·7H 2 O is prepared into a salt solution (feeding) with the concentration of 2.5mol/L according to the molar ratio of 0.65 0.65 Co 0.12 Mn 0.225 Fe 0.005 (OH) 2 Washing with 5 mol/L60 deg.C hot NaOH solution and 50 deg.C pure water for 20min and 10min respectively, wherein the volumes of the precursor slurry, alkali solution and pure waterAnd 4.
Example 5
The embodiment prepares the cathode material, and the specific steps are as follows:
D1. the precursor of the cathode material obtained in example 1, liOH and a bulk phase doping additive ZrO 2 、Y 2 O 3 After being uniformly mixed, the mixture is sintered in the atmosphere with the oxygen concentration of 95 percent, the sintering period is 27h, and the temperature is kept at 940 ℃ for 12h;
wherein the proportion of the anode material precursor to LiOH is that the molar ratio of Li/(Ni + Co + Mn + Fe) is 1.05;
additive ZrO 2 And Y 2 O 3 In amounts of 3000ppm and 1500ppm, respectively (as ZrO) 2 /Y 2 O 3 The Zr/Y accounts for the mass of the precursor).
D2. The product obtained in the step D1 is subjected to coarse crushing and fine crushing (the D50 particle size of the obtained intermediate product is about 4 mu m) and then is mixed with an additive WO 3 And Al 2 O 3 Uniformly mixing, performing secondary sintering in the atmosphere of 95% oxygen concentration, wherein the sintering period is 15h, and the temperature is kept at 550 ℃ for 6h, wherein WO 3 And Al 2 O 3 In amounts of 1500ppm and 1000ppm, respectively (in WO) 3 /Al 2 O 3 Wherein W/Al is based on the weight of the product obtained in the step D1).
Example 6
The embodiment prepares the cathode material, and the specific steps are as follows:
D1. the precursor of the cathode material obtained in example 2, liOH and a bulk phase doping additive ZrO 2 And after uniformly mixing the SrO, sintering the mixture in an atmosphere with the oxygen concentration of 97 percent, wherein the sintering period is 29h, and the temperature of 830 ℃ is kept for 15h.
Wherein the proportion of the precursor of the positive electrode material to LiOH is that the molar ratio of Li/(Ni + Co + Mn + Fe) is 1.03;
additive ZrO 2 And SrO were added in amounts of 2000ppm and 800ppm (as ZrO) respectively 2 Zr/Sr in/SrO accounts for the mass of the precursor).
D2. The product obtained in the step D1 is subjected to coarse crushing and fine crushing until the D50 is about 4 mu m, and then is mixed with an additive Sb 2 O 3 And TiO 2 MixingUniformly sintering the mixture for the second time in the atmosphere with 97 percent of oxygen concentration, wherein the sintering period is 14h, and the temperature is kept at 400 ℃ for 5h, wherein Sb is 2 O 3 And TiO 2 Are added in amounts of 1000ppm and 2000ppm (as Sb) 2 O 3 /TiO 2 Wherein Sb/Ti is the weight of the product obtained in the step D1).
Example 7
The embodiment prepares the cathode material, and the specific steps are as follows:
D1. the precursor of the cathode material obtained in example 3, liOH and bulk phase doping additive CeO 2 And La 2 O 3 After being mixed evenly, the mixture is sintered under the atmosphere with the oxygen concentration of 99 percent, the sintering period is 30h, and the temperature is kept at 750 ℃ for 16h. (ii) a
Wherein the proportion of the precursor of the positive electrode material to LiOH is that the molar ratio of Li/(Ni + Co + Mn + Fe) is 1.01;
additive CeO 2 And La 2 O 3 The amounts of (B) added were 1500ppm and 1500ppm (as CeO) 2 And La 2 O 3 Meter for measuring Ce and La in the mass of precursor
D2. The product obtained in the step D1 is subjected to coarse crushing and fine crushing until the D50 is about 4 mu m, and then is mixed with an additive Nb 2 O 5 And B 2 O 3 Mixing uniformly, sintering twice in the atmosphere of 97% oxygen concentration, the sintering period is 1697 deg.C, keeping the temperature for 8 hours, wherein Nb 2 O 5 And B 2 O 3 The amounts of addition of (B) are 1500ppm and 1000ppm (as Nb) 2 O 5 /B 2 O 3 Wherein Nb/B is based on the weight of the product obtained in the step D1).
Example 8
The embodiment prepares the cathode material, and the specific steps are as follows:
D1. the precursor of the positive electrode material obtained in example 4 was mixed with Li 2 CO 3 Additive MoO 3 And ZrO 2 After being uniformly mixed, the mixture is sintered in the atmosphere with the oxygen concentration of 90 percent, the sintering period is 32h, and the temperature is kept at 950 ℃ for 15h;
wherein the positive electrode material precursor and Li 2 CO 3 The ratio of (A) is Li/(Ni + Co + Mn + Fe) =1.06;
additive MoO 3 And ZrO 2 In the amounts of 1000ppm and 2000ppm (in terms of MoO), respectively 3 /ZrO 2 The mass of the medium Mo/Zr in the positive electrode material precursor);
D2. the product obtained in the step D1 is subjected to coarse crushing and fine crushing until the D50 is about 4 mu m, and then is mixed with an additive MgCO 3 Mixing with NaF, sintering at 90% oxygen concentration for 5 hr with sintering period of 1693 deg.C, and maintaining at 700 deg.C for MgCO 3 And NaF were added in amounts of 2000ppm and 1000ppm (as MgCO) 3 Mg/F in NaF based on the weight of the product of step D1).
Comparative example 1
This comparative example prepared a precursor of a positive electrode material, which was different from example 1 in that:
the solute in the salt solution is composed of NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is mixed according to a molar ratio of 0.70.
Comparative example 2
This comparative example prepared a precursor of a positive electrode material, which was different from example 2 in that:
the solute in the salt solution is composed of NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is mixed according to a molar ratio of 0.70.
Comparative example 3
This comparative example prepared a precursor of a positive electrode material, which was different from example 3 in that:
the solute in the salt solution is composed of NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is mixed according to a molar ratio of 0.92.
Comparative example 4
This comparative example prepared a precursor of a positive electrode material, which was different from example 4 in that:
the solute in the salt solution is composed of NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 According to the molar ratio of O0.65.
Comparative example 5
This comparative example prepared a precursor of a positive electrode material, which was different from example 1 in that:
FeSO in salt solution 4 ·7H 2 Replacing O with ZrSO of equimolar concentration 4 ·4H 2 O, the design chemical formula of the precursor of the obtained cathode material is Ni 0.70 Co 0.05 Mn 0.247 Zr 0.003 (OH) 2 。
Comparative example 6
This comparative example prepared a precursor of a positive electrode material, which was different from example 3 in that:
the solute in the salt solution is composed of NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O、ZrSO 4 ·4H 2 O、FeSO 4 ·7H 2 O, 0.04, and 0.01;
the design chemical formula of the precursor of the positive electrode material of the comparative example is Ni 0.90 Co 0.04 Mn 0.04 Zr 0.01 Fe 0.01 (OH) 2 。
Comparative example 7
This comparative example prepared a precursor of a positive electrode material, which was different from example 1 in that:
the solute in the salt solution is composed of NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O、FeSO 4 ·7H 2 O、FeSO 4 ·7H 2 O is mixed according to a molar ratio of 0.70.
Comparative example 8
This comparative example prepared a positive electrode material, which was different from example 5 in that:
the positive electrode material precursor used in this comparative example was from comparative example 1.
Comparative example 9
This comparative example prepared a positive electrode material, which was different from example 6 in that:
the positive electrode material precursor used in this comparative example was from comparative example 2.
Comparative example 10
This comparative example prepared a positive electrode material, which was different from example 7 in that:
the precursor of the positive electrode material used in this comparative example was derived from comparative example 3.
Comparative example 11
This comparative example prepared a positive electrode material, which was different from example 8 in that:
the positive electrode material precursor used in this comparative example was from comparative example 4.
Comparative example 12
This comparative example prepared a positive electrode material, which was different from example 5 in that:
the positive electrode material precursor used in this comparative example was from comparative example 5.
Comparative example 13
This comparative example prepared a positive electrode material, which was different from example 7 in that:
the positive electrode material precursor used in this comparative example was from comparative example 6.
Test example
In the first aspect of the test example, the content of sulfur impurity in the precursor of the positive electrode material obtained in examples 1 to 4 and comparative examples 1 to 7 was measured by the following method: the test was performed using inductively coupled plasma emission spectroscopy (ICP-AES).
The test results are shown in table 1.
Figure BDA0003763204540000111
As can be seen from comparison between examples 1 to 4 and comparative examples 1 to 4, if the same preparation method is adopted, and if Fe doping is not performed, the content of sulfur as an impurity in the precursor of the positive electrode material is significantly increased, which indicates that the content of S in the precursor of the positive electrode material can be significantly reduced by Fe doping, and guarantees are provided for performance improvement of the subsequent positive electrode material.
Comparison of examples 1 to 5 also shows that, although the preparation methods are similar, the positive electrode material/positive electrode material precursor compositions are different, and the impurity sulfur content of the obtained positive electrode material precursor is different, and tends to increase with the increase in Ni content.
As can be seen from comparison of example 1, comparative example 1, and comparative example 5, if Fe is doped with Zr in an equal amount, the content of impurity sulfur in the precursor of the positive electrode material is increased, which indicates that the presence of Zr adversely affects the decrease in the content of impurity sulfur.
Comparing example 1 with comparative example 7, it is understood that the effect of reducing the content of impurity sulfur can be achieved only by doping Fe within the range provided by the present invention, which is higher than the range provided by the present invention, but the opposite result is obtained.
Example 2 and comparative example 6 compare to see that: further improving the doping amount of Fe, and increasing the reduction amplitude of the S content in the precursor.
Meanwhile, the content of magnetic impurities in the precursors of the positive electrode materials obtained in examples 1 to 4 and comparative examples 1 to 7 was also tested in this test example, and the test method was as listed in the international document "determination of content of magnetic foreign matter and content of residual alkali in positive electrode material for lithium ion battery" (examination draft).
The test results show that the magnetic impurity content of the positive electrode material precursor obtained in other examples and comparative examples is less than 50ppb, and the magnetic impurity content of the positive electrode material precursor obtained in comparative example 7 exceeds 200ppb, so that the requirement of subsequent preparation of the positive electrode material is obviously not met, and further test, characterization and use are not carried out. Therefore, if the doping amount of Fe in the precursor of the cathode material is beyond the range provided by the invention, the magnetic impurities are easy to exceed the standard.
In a second aspect of the present test example, the morphology of the precursor of the positive electrode material obtained in example 1, the morphology of the positive electrode material obtained in example 5, and the morphology of the precursor of the positive electrode material obtained in comparative example 1 were characterized. The results show that the positive electrode material precursors obtained in example 1 and comparative example 1 have similar morphologies, which indicates that the morphology of the positive electrode material precursor is not affected by a small amount of doped Fe. The positive electrode material obtained by calcining the precursor of the positive electrode material obtained in example 1 has a single crystal structure. Specific results are shown in FIGS. 1 to 2 and 4.
The test example also tests the appearances of the positive electrode materials and the positive electrode material precursors obtained in other examples, wherein the specific appearance of the positive electrode material precursor is similar to that of the example, and the appearance of the positive electrode material is similar to that of the example 5.
In the third aspect of the present test example, the Li/Ni mixed-segregation degree of the positive electrode materials obtained in examples 5 to 8 and comparative examples 8 to 13 was tested by obtaining XRD patterns of the respective positive electrode materials, and then refining the obtained XRD patterns by using fullprrof software to obtain the Li/Ni mixed-segregation value.
The XRD spectrum (and the corresponding refined spectrum) of the cathode material obtained in example 5 of the present invention is shown in fig. 3, and it can be seen from the graph that the refined spectrum has a higher degree of coincidence with the XRD original test data, which indicates that the fullprrof refined result has a higher reliability.
The results of Li/Ni mixed-out of each positive electrode material are shown in table 2.
The fourth aspect of this test example tested the electrochemical performance of the positive electrode materials obtained in examples 5 to 8 and comparative examples 8 to 13 by the following methods:
the method comprises the steps of uniformly mixing a positive electrode material, acetylene black and PVDF according to the mass ratio of 9.2: 0.5: 0.3 by taking N-methyl pyrrolidone as a solvent to form slurry, coating the slurry on an aluminum foil, drying by blowing at 80 ℃ for 8 hours, and drying at 120 ℃ for 12 hours in vacuum to obtain the positive electrode.
Assembling the battery in an argon-protected glove box, wherein the negative electrode is a metal lithium sheet, the diaphragm is a polypropylene film, and the electrolyte is 1MLiPF 6 EC/DMC (1: 1,v/v), 2032 type button cell case.
The test voltage is 2.8-4.35V for example 5, example 8, comparative example 8 and comparative examples 11-12; 2.8-4.25V is adopted in examples 6-7, comparative examples 9-10 and comparative example 13, the charge-discharge multiplying power of the cycle test is 0.1C, and the cycle number is 100 weeks; in the rate test, test specific capacities in terms of discharge (average value of 5-week test) of 0.2C, 0.5C, 1C, 2C and 5C were tested. The test results are shown in tables 2 to 3.
TABLE 2 partial performance results of the cathode materials obtained in examples 5 to 8 and comparative examples 8 to 13
Figure BDA0003763204540000121
Figure BDA0003763204540000131
TABLE 3 Rate Properties of Positive electrode materials obtained in examples 5 to 8 and comparative examples 8 to 13
0.2C(mAh/g) 0.5C(mAh/g) 1C(mAh/g) 2C(mAh/g) 5C(mAh/g)
Example 5 199 193 185 172 159
Comparative example 8 187 176 164 149 132
Comparative example 12 186 177 162 147 129
Example 6 207 202 193 182 171
Comparative example 9 197 189 178 166 152
Example 7 227 223 217 205 191
Comparative example 10 214 206 196 182 165
Comparative example 13 205 197 183 166 152
Example 8 191 185 178 169 160
Comparative example 11 182 175 166 157 143
The results of tables 2 and 3 show that:
compared with the positive electrode material not doped with Fe, the reduction range of the Li/Ni mixed row of the positive electrode material provided by the invention is 33-45% (comparing examples 5-8 with comparative examples 8-11. Similarly, the first cycle specific capacity, the first efficiency, the cycle performance and the rate capability of the corresponding positive electrode material are all improved.
The doping of Fe can improve the ordered degree of atomic arrangement in the anode material and can also improve the overall electrochemical performance of the obtained anode material.
The comparison result between example 5 and comparative example 12 shows that if Fe doping is replaced by equal amount of Zr doping, the performance of the cathode material is reduced, which indicates that the zirconium doping in the amount has negative effect on the performance of the cathode material.
The comparison result between the example 7 and the comparative example 13 shows that if the doping amount of Fe is increased and Zr is doped at the same time, the performance of the obtained cathode material is also inferior to that of the cathode material provided by the invention.
According to the results, the precursor of the cathode material provided by the invention has low impurity sulfur content, the cathode material prepared from the precursor has excellent electrochemical performance, and the precursor is expected to be used for preparing secondary batteries, and the obtained secondary batteries are expected to be used as power batteries, energy storage batteries and the like.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. A positive electrode material precursor is characterized by comprising a substance represented by the following chemical formula:
Ni x Co y Mn z Fe a (OH) 2 ；
wherein 0<x is less than 1; y is more than or equal to 0 and less than or equal to 0.9; z is more than or equal to 0 and less than or equal to 0.9;0<a is not more than 0.005; x + y + z + a =1.
2. The positive electrode material precursor according to claim 1, wherein Ni is Ni x Co y Mn z Fe a (OH) 2 In the formula, a is more than or equal to 0.001 and less than or equal to 0.005.
3. A method for preparing a precursor of the positive electrode material according to claim 1 or 2, comprising mixing a salt solution, ammonia water and an alkali solution for reaction;
the salt solution contains nickel ions, cobalt ions, manganese ions and iron ions;
the mass ratio of the nickel ions, the cobalt ions, the manganese ions and the iron ions is x: y: z: a.
4. the method of claim 3, wherein the salt solution has a concentration of 1 to 3mol/L; preferably, the concentration of the ammonia water is 0.5-12 g/L; preferably, the pH value in the system of the mixed reaction is 8.5-12.
5. A positive electrode material, characterized in that a raw material for producing the positive electrode material comprises the positive electrode material precursor according to claim 1 or 2.
6. The positive electrode material according to claim 5, wherein the positive electrode material has a chemical formula shown below:
Li 1+b Ni x Co y Mn z Fe a M c O 2 ；
wherein B is more than or equal to 0 and less than or equal to 0.2,0 and less than or equal to 0.03, M is at least two of Ni, co, mn, zr, al, mg, ti, sr, W, Y, mo, sb, nb, sn, zn, la, ce, B and F.
7. The cathode material according to claim 6, wherein the raw material for preparing the cathode material further comprises at least one of a bulk phase dopant, a surface dopant and a surface coating agent.
8. A method for preparing the positive electrode material according to any one of claims 5 to 7, comprising mixing the positive electrode material precursor and a lithium source and then sequentially performing the first sintering and the second sintering.
9. A secondary battery, characterized in that a raw material for producing the secondary battery comprises the positive electrode material according to any one of claims 5 to 7.
10. Use of a secondary battery according to claim 9 in the field of power batteries and in the field of energy storage.
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