CN107275632B - lithium ion battery anode precursor material with low lattice stress and preparation method thereof - Google Patents
lithium ion battery anode precursor material with low lattice stress and preparation method thereof Download PDFInfo
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Abstract
A lithium ion battery anode precursor material with low lattice stress and a preparation method thereof. The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium ion battery anode precursor material with low lattice stress and a preparation method thereof. The invention aims to solve the problems that the lattice stress is generated due to the change of the proportion of transition metal elements in the ternary gradient precursor material for preparing the anode material of the lithium ion battery at present, so that the lattice stress of the prepared ternary anode material is higher, and the cycle stability and the rate capability of the electrode material are influenced. The method comprises the following steps: firstly, preparing a mixed metal salt water solution; secondly, preparing a precipitator aqueous solution; thirdly, preparing a complexing agent for dissolving in water; fourthly, preparing a fluoride aqueous solution; fifthly, preparing a precursor material; sixthly, cooling. The content of Ni and F in the lithium ion battery anode precursor material is in reverse gradient change, so that the lattice stress is effectively reduced, and the cycle performance and the rate capability are improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium ion battery anode precursor material with low lattice stress and a preparation method thereof.
background
since the commercialization of lithium ion batteries in the 90 s of the 20 th century, lithium ion batteries have rapidly become the most important and most widely used secondary batteries. Through the development of many years, the lithium ion battery is widely applied to various small portable electronic products and electric tools, and is gradually applied to the new energy automobile market in a large amount along with the recent increase of attention on energy in various countries in the world. The anode material is one of the key materials for manufacturing the lithium ion battery, and because the specific capacity of the common anode material is obviously lower than that of the cathode material, the performance of the anode material directly influences various indexes of the final battery. Therefore, it is extremely important to develop a positive electrode material.
Lithium cobaltate (LiCoO 2) is a positive electrode material used in the first commercial lithium ion battery of Sony corporation, and is still the mainstream material in the current lithium ion battery market at present, but because cobalt toxicity is high, price is high, and excessive Li + which is extracted aggravates structural instability caused by oxygen layer repulsion, so that cost and safety problems are caused, people are always searching for better alternative materials.
in contrast, the nickel cobalt lithium manganate ternary material (LiNi x Co y Mn z O 2) has a single-phase layered structure similar to LiCoO 2, based on the synergistic effect between transition metals, the ternary metal oxide material combines the good rate capability of LiCoO 2, the high capacity of LiNiO 2 and the structural stability obtained due to the existence of Mn 4+.
However, the high nickel ternary material has high capacity due to high nickel content, and the structure and thermal stability of the high nickel material in a lithium-removed state are not ideal, and in addition, with the increase of the nickel content, a serious lithium-nickel mixed-discharging phenomenon is caused, so that the cycle performance of the material is poor. Therefore, researchers develop the ternary material with gradient change from inside to outside, and the gradient material has the advantages of good material cycle performance and high specific capacity due to the gradient change of components from inside to outside.
however, due to different ionic radii of different transition metals, lattice parameters of ternary cathode materials with different metal proportions are different, and due to the fact that transition metal elements of the high-nickel gradient cathode material are in gradient change, lattice parameters of the gradient cathode materials are not matched, lattice stress exists on a microstructure, so that the high-nickel gradient cathode material is easy to pulverize and break in the charge-discharge cycle process of the material, electrical contact between the cathode materials is reduced, stress resistance strength of the electrode material is influenced, and cycle stability and rate capability of the material are reduced, and therefore the simple method for improving the stress resistance of the high-nickel gradient ternary material is significant.
disclosure of Invention
the invention aims to solve the problems that the lattice stress is generated due to the change of the proportion of transition metal elements in a ternary gradient precursor material for preparing a lithium ion battery anode material at present, so that the prepared ternary anode material has higher lattice stress and the cycling stability and the rate capability of an electrode material are influenced, and provides a lithium ion battery anode precursor material with low lattice stress and a preparation method thereof.
the chemical formula of the lithium ion battery anode precursor material with low lattice stress is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n, wherein the content x of Ni is reduced in a gradient manner from inside to outside, the content n of F is increased in a gradient manner from inside to outside, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + y + z is more than 0 and less than or equal to 1, and n is more than 0 and less than or equal to 0.15.
The preparation method of the lithium ion battery anode precursor material with low lattice stress is carried out according to the following steps:
1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 2Firstly, mixing nickel salt, cobalt salt, manganese salt and M salt according to a molar ratio to prepare a mixed metal brine solution A, wherein the concentration of the mixed metal salt in the mixed metal brine solution A is 0.01-20 mol/L, the molar ratio of nickel element to cobalt element to manganese element to M element is x: y: z (1-x-y-z), wherein x is not less than 0 and not more than 1, y is not less than 0 and not more than 1, z is not less than 0 and not more than 1, x + y + z is not more than 0 and not more than 1, mixing nickel salt, cobalt salt, manganese salt and M salt according to a molar ratio to prepare a mixed metal brine solution B, the concentration of the mixed metal salt in the mixed metal brine solution B is 0.01-20 mol/L, the molar ratio of nickel element to manganese element to M element is not less than x: y: z (1-x-y-z), wherein x is not more than 0 and not more than 1, y is not more than 0 and not more than 1, and z is not more than 1 when x-z is not more than 1 and x-y-z;
secondly, preparing a precipitant aqueous solution: mixing a precipitator with water to prepare a precipitator aqueous solution with the concentration of 0.01-20 mol/L;
Thirdly, preparing a complexing agent aqueous solution: mixing a complexing agent with water to prepare a complexing agent aqueous solution A; the concentration of the complexing agent in the complexing agent aqueous solution A is 0.01-20 mol/L; mixing complexing agent with water to prepare complexing agent water solution B; the concentration of the complexing agent in the complexing agent water solution B is 0.01-10 mol/L;
fourthly, preparing a fluoride aqueous solution: mixing fluoride with water to prepare a fluoride aqueous solution A; the concentration of fluoride in the fluoride aqueous solution A is 0.001 mol/L-2 mol/L; ② mixing fluoride with water to prepare a fluoride water solution B; the concentration of the fluoride in the fluoride aqueous solution B is 0-2 mol/L;
Fifthly, preparing a precursor material: adding the water solution B of the complexing agent in the third step into a continuous stirring liquid phase reactor to be used as reaction base liquid, and then carrying out the following steps of: respectively and continuously injecting a mixed metal salt aqueous solution A, a precipitant aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as primary feeding materials under the conditions of inert atmosphere, pH value of 4-14, constant temperature of 10-85 ℃ and rotation speed of 600-1000 r/min, respectively injecting a mixed metal salt aqueous solution A, a precipitant aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as secondary feeding materials while injecting the primary feeding materials, respectively and continuously injecting a mixed metal salt aqueous solution B and a fluoride aqueous solution B into the mixed metal salt aqueous solution A and the fluoride aqueous solution A, wherein the primary feeding materials and the secondary feeding materials are added continuously for the whole preparation process, when the reaction is carried out until the solid-liquid mass ratio in the continuous stirring liquid phase reactor is 1/40-1/5, the rotation speed is adjusted from 600 r/min-1000 r/min, the adjustment range is 200r/, opening an overflow pipe to overflow, wherein the overflow amount is the feeding amount in the time of the step (III), so that the amount of the solution in the continuous stirring liquid phase reactor is recovered to the amount of the solution at the starting moment of the step (III), repeating the step (IV) until the total reaction time is 5-30 h, stopping the addition of the primary feeding and the secondary feeding at the moment, and stopping heating to finish the preparation of the precursor material;
in the fifth step, the volume of the complexing agent aqueous solution B is 10-80% of the volume of the continuous stirring liquid phase reactor;
feeding rate ratios of the four substances of the primary feed in the fifth step are that when the chemical formula of the precursor material is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n, the feeding rate ratio of the mixed metal saline solution A to the precipitant aqueous solution to the complexing agent aqueous solution A to the fluoride aqueous solution A is 1:2:1:1, and when the chemical formula of the precursor material is Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n, the feeding rate ratio of the mixed metal saline solution A to the precipitant aqueous solution to the complexing agent aqueous solution A to the fluoride aqueous solution A is 1:1:1: 1;
fifthly, the feeding rates of the mixed metal salt water solution B and the mixed metal salt water solution A are the same; the feeding rate of the primary feeding aqueous fluoride solution B is the same as that of the aqueous fluoride solution A;
in the fifth step, the ratio of the total moles of the complexing agent in the complexing agent aqueous solution A, B to the total moles of the metal salt in the mixed metal salt aqueous solution A, B is 0.1-10.0: 1; the ratio of the mole number of the precipitant in the precipitant aqueous solution to the total mole number of the metal salt in the mixed metal salt aqueous solution A, B is 0.1-4.0: 1; the ratio of the total moles of fluoride in the aqueous fluoride solution A, B to the total moles of metal salts in the aqueous mixed metal salt solution A, B is 0.001-2.0: 1;
and sixthly, cooling, namely stirring for 1-3 hours at the rotating speed of 500-1000 r/min to reduce the temperature of the continuous stirring liquid phase reactor to room temperature, thus obtaining the lithium ion battery anode precursor material Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n with low lattice stress.
The invention has the beneficial effects that:
1. According to the invention, by controlling the content change of Ni and F in a precursor material Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n for the anode material of the lithium ion battery, the increase of the Ni element can reduce the lattice parameter in a certain range, and the increase of the F element can increase the lattice parameter to make up the reduction of the lattice parameter caused by the reduction of the Ni content, so that the inner lattice parameter and the outer lattice parameter of the gradient fluorine-doped ternary gradient material are consistent and lattice-matched, the lattice stress of the prepared oxide anode material is effectively reduced, and the internal stress is small.
2. According to the invention, a two-stage feeding mode is adopted, the uniform gradient change of the metal element and the F element is realized simultaneously, and the characteristic of uniform stirring by a coprecipitation method is utilized, so that the accuracy and controllability of the chemical composition of the material are ensured.
3. The precursor material doped with the gradient F prepared by the invention is used for preparing the oxide anode material, and the solid phase sintering temperature of the ternary gradient anode material is reduced by utilizing the fluxing agent characteristic of the metal fluoride, so that the energy is saved.
4. The preparation process is simple, the material cost is low, and the method is suitable for industrial production.
Drawings
Fig. 1 is an SEM image of a lithium ion battery positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 prepared in test one;
FIG. 2 is a schematic diagram showing a comparison of lattice structures of ternary cathode materials before and after gradient fluorine doping in a first verification test;
FIG. 3 is an SEM image of a gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared by the verification test I in the third step;
FIG. 4 is an XRD (X-ray diffraction) diagram of a gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared by the verification test I in the fourth step;
fig. 5 is a first charge-discharge curve diagram of the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared in the first verification test (v) at a magnification of 0.1C;
fig. 6 is a rate performance curve diagram of the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared by the verification test one in (vi);
FIG. 7 is a graph of comparative cycle performance at 1C rate of the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared in the verification test I and the control gradient ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 2 in (VII);
fig. 8 is an SEM image of the gradient fluorine-doped ternary positive electrode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared by the verification test one in (eight) after 200 cycles at a magnification of 1C;
Fig. 9 is an SEM image of the control gradient ternary positive electrode material LiNi 0.481 Co 0.193 Mn 0.289 O 2 in (eight) after 200 cycles at 1C magnification.
Detailed Description
in a first specific embodiment, the chemical formula of the lithium ion battery positive electrode precursor material with low lattice stress is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n, wherein the content x of Ni is reduced in a gradient manner from inside to outside, the content n of F is increased in a gradient manner from inside to outside, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + y + z is more than 0 and less than or equal to 1, and n is more than 0 and less than or equal to 0.15.
The second embodiment is different from the first embodiment in that the gradient of the change of the content x of Ni and the gradient of the change of the content n of F satisfy 5 ≦ Δ x/Δ n ≦ 7, wherein Δ x is the difference of the content x of Ni at different distances from the center of the sphere, Δ n is the difference of the content n of F at the position corresponding to the content x of Ni.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: and M is one or a mixture of more of Li, Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi. Other steps and parameters are the same as those in the first or second embodiment.
the fourth concrete implementation mode: the preparation method of the lithium ion battery anode precursor material with low lattice stress of the embodiment comprises the following steps:
1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 2firstly, mixing nickel salt, cobalt salt, manganese salt and M salt according to a molar ratio to prepare a mixed metal brine solution A, wherein the concentration of the mixed metal salt in the mixed metal brine solution A is 0.01-20 mol/L, the molar ratio of nickel element to cobalt element to manganese element to M element is x: y: z (1-x-y-z), wherein x is not less than 0 and not more than 1, y is not less than 0 and not more than 1, z is not less than 0 and not more than 1, x + y + z is not more than 0 and not more than 1, mixing nickel salt, cobalt salt, manganese salt and M salt according to a molar ratio to prepare a mixed metal brine solution B, the concentration of the mixed metal salt in the mixed metal brine solution B is 0.01-20 mol/L, the molar ratio of nickel element to manganese element to M element is not less than x: y: z (1-x-y-z), wherein x is not more than 0 and not more than 1, y is not more than 0 and not more than 1, and z is not more than 1 when x-z is not more than 1 and x-y-z;
Secondly, preparing a precipitant aqueous solution: mixing a precipitator with water to prepare a precipitator aqueous solution with the concentration of 0.01-20 mol/L;
Thirdly, preparing a complexing agent aqueous solution: mixing a complexing agent with water to prepare a complexing agent aqueous solution A; the concentration of the complexing agent in the complexing agent aqueous solution A is 0.01-20 mol/L; mixing complexing agent with water to prepare complexing agent water solution B; the concentration of the complexing agent in the complexing agent water solution B is 0.01-10 mol/L;
Fourthly, preparing a fluoride aqueous solution: mixing fluoride with water to prepare a fluoride aqueous solution A; the concentration of fluoride in the fluoride aqueous solution A is 0.001 mol/L-2 mol/L; ② mixing fluoride with water to prepare a fluoride water solution B; the concentration of the fluoride in the fluoride aqueous solution B is 0-2 mol/L;
Fifthly, preparing a precursor material: adding the water solution B of the complexing agent in the third step into a continuous stirring liquid phase reactor to be used as reaction base liquid, and then carrying out the following steps of: respectively and continuously injecting a mixed metal salt aqueous solution A, a precipitant aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as primary feeding materials under the conditions of inert atmosphere, pH value of 4-14, constant temperature of 10-85 ℃ and rotation speed of 600-1000 r/min, respectively injecting a mixed metal salt aqueous solution A, a precipitant aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as secondary feeding materials while injecting the primary feeding materials, respectively and continuously injecting a mixed metal salt aqueous solution B and a fluoride aqueous solution B into the mixed metal salt aqueous solution A and the fluoride aqueous solution A, wherein the primary feeding materials and the secondary feeding materials are added continuously for the whole preparation process, when the reaction is carried out until the solid-liquid mass ratio in the continuous stirring liquid phase reactor is 1/40-1/5, the rotation speed is adjusted from 600 r/min-1000 r/min, the adjustment range is 200r/, opening an overflow pipe to overflow, wherein the overflow amount is the feeding amount in the time of the step (III), so that the amount of the solution in the continuous stirring liquid phase reactor is recovered to the amount of the solution at the starting moment of the step (III), repeating the step (IV) until the total reaction time is 5-30 h, stopping the addition of the primary feeding and the secondary feeding at the moment, and stopping heating to finish the preparation of the precursor material;
In the fifth step, the volume of the complexing agent aqueous solution B is 10-80% of the volume of the continuous stirring liquid phase reactor;
Feeding rate ratios of the four substances of the primary feed in the fifth step are that when the chemical formula of the precursor material is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n, the feeding rate ratio of the mixed metal saline solution A to the precipitant aqueous solution to the complexing agent aqueous solution A to the fluoride aqueous solution A is 1:2:1:1, and when the chemical formula of the precursor material is Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n, the feeding rate ratio of the mixed metal saline solution A to the precipitant aqueous solution to the complexing agent aqueous solution A to the fluoride aqueous solution A is 1:1:1: 1;
Fifthly, the feeding rates of the mixed metal salt water solution B and the mixed metal salt water solution A are the same; the feeding rate of the primary feeding aqueous fluoride solution B is the same as that of the aqueous fluoride solution A;
In the fifth step, the ratio of the total moles of the complexing agent in the complexing agent aqueous solution A, B to the total moles of the metal salt in the mixed metal salt aqueous solution A, B is 0.1-10.0: 1; the ratio of the mole number of the precipitant in the precipitant aqueous solution to the total mole number of the metal salt in the mixed metal salt aqueous solution A, B is 0.1-4.0: 1; the ratio of the total moles of fluoride in the aqueous fluoride solution A, B to the total moles of metal salts in the aqueous mixed metal salt solution A, B is 0.001-2.0: 1;
Sixthly, cooling, namely stirring for 1-3 h under the condition that the rotating speed is 500-1000 r/min to reduce the temperature of the continuously stirred liquid phase reactor to room temperature, thus obtaining the lithium ion battery anode precursor material Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n with low lattice stress.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: in the first step, the nickel salt is one or a mixture of more of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride. Other steps and parameters are the same as those in the fourth embodiment.
The sixth specific implementation mode: the present embodiment is different from the fourth or fifth embodiment in that: the cobalt salt is one or a mixture of more of cobalt sulfate, cobalt nitrate, cobalt acetate and cobalt chloride. Other steps and parameters are the same as those in one of the fourth or fifth embodiments.
The seventh embodiment: this embodiment differs from one of the fourth to sixth embodiments in that: the manganese salt is one or a mixture of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride. Other steps and parameters are the same as those in one of the fourth to sixth embodiments.
The specific implementation mode is eight: this embodiment is different from one of the fourth to seventh embodiments in that: in the step one, the M salt is one or a mixture of more of soluble sulfate, soluble nitrate, soluble acetate, soluble chloride, soluble citrate and soluble alkoxide; wherein M is one or a mixture of more of Li, Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi. Other steps and parameters are the same as those of one of the fourth to seventh embodiments.
ninth embodiment, the difference between the fourth to eighth embodiments is that in the second step, when the precursor material is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n, one or a mixture of several of sodium hydroxide, potassium hydroxide and lithium hydroxide is used as the precipitant.
embodiment ten the difference between this embodiment and one of the fourth to ninth embodiments is that when the precursor material in the second step is Ni x Co y Mn z M 1-x-y-z (Co 3) 1-0.5n F n, the precipitant is one or a mixture of several of sodium carbonate, potassium carbonate and lithium carbonate.
The concrete implementation mode eleven: the present embodiment is different from one of the fourth to tenth embodiments in that: in the third step, the complexing agent is one or a mixture of more of ammonia water, ammonium chloride, ammonium fluoride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid and malonic acid. Other steps and parameters are the same as those in one of the fourth to tenth embodiments.
the specific implementation mode twelve: this embodiment is different from one of the fourth to eleventh embodiments in that: the fluoride in the fourth step is one or a mixture of sodium fluoride, potassium fluoride and ammonium chloride. Other steps and parameters are the same as those of one of the fourth to eleventh embodiments.
thirteenth embodiment is different from the fourth to twelfth embodiments in that the precursor material Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n with low lattice stress is obtained in the sixth embodiment, wherein the content x of Ni is changed in a gradient from inside to outside, the content n of F is changed in a gradient opposite to x from inside to outside, 0< x ≦ 1, 0< y ≦ 1, 0< z ≦ 1, 0< x + y + z ≦ 1, 0< n ≦ 0.15, and other steps and parameters are the same as those of the fourth to twelfth embodiments.
the following experiments were conducted to verify the effects of the present invention
The first test and the preparation method of the lithium ion battery anode precursor material with low lattice stress are carried out according to the following steps:
Firstly, preparing a mixed metal salt aqueous solution: mixing nickel sulfate, cobalt sulfate, manganese sulfate and lithium sulfate according to a molar ratio to prepare a mixed metal salt water solution A; the concentration of the mixed metal salt in the mixed metal salt water solution A is 2 mol/L; the molar ratio of the mixed metal salt aqueous solution A is nickel element: cobalt element: manganese element: lithium element 2.7: 0.9: 5.4: 1; mixing nickel sulfate, cobalt sulfate, manganese sulfate and lithium sulfate according to a molar ratio to prepare a mixed metal salt water solution B; the concentration of the mixed metal salt in the mixed metal salt water solution B is 2 mol/L; the molar ratio of the mixed metal salt aqueous solution B is nickel element: cobalt element: manganese element: lithium element 3: 3: 3: 1;
Secondly, preparing a precipitant aqueous solution: mixing sodium hydroxide with water to prepare a precipitant aqueous solution with the concentration of the sodium hydroxide of 2 mol/L;
Thirdly, preparing a complexing agent aqueous solution: firstly, ammonia water is mixed with water to prepare a complexing agent aqueous solution A; the concentration of ammonia water in the complexing agent aqueous solution A is 2.8 mol/L; secondly, mixing ammonia water and water to prepare a complexing agent aqueous solution B; the concentration of ammonia water in the complexing agent aqueous solution B is 0.3 mol/L;
Fourthly, preparing a fluoride aqueous solution: firstly, mixing ammonium fluoride with water to prepare a fluoride aqueous solution A; the concentration of ammonium fluoride in the fluoride aqueous solution A is 0.01 mol/L; secondly, mixing ammonium fluoride with water to prepare a fluoride water solution B; the concentration of ammonium fluoride in the fluoride aqueous solution B is 0.15 mol/L;
Fifthly, preparing a precursor material: adding the water solution B of the complexing agent in the third step into a continuous stirring liquid phase reactor to be used as reaction base liquid, and then carrying out the following steps of: respectively and continuously injecting a mixed metal saline solution A, a precipitator aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as primary feeding materials under the conditions of inert atmosphere, pH value of 10 +/-0.3, constant temperature of 60 ℃ and rotation speed of 900r/min, respectively injecting a mixed metal saline solution B and a fluoride aqueous solution B into a mixed metal saline solution A and a fluoride aqueous solution A as secondary feeding materials while injecting the primary feeding materials, respectively and continuously injecting the mixed metal saline solution B and the fluoride aqueous solution B into the whole preparation process, regulating the rotation speed from 900r/min to 300r/min after the reaction is carried out for 1h, reacting for 2h at the regulated rotation speed, opening an overflow pipe to start overflowing, wherein the overflowing amount is the feeding amount within 2h in the step III, and recovering the amount of the solution in the continuous stirring liquid phase reactor to the solution amount at the starting time in the step III, fifthly, repeating the step IV until the total reaction time is 12 hours, stopping adding the primary feeding and the secondary feeding at the moment, and stopping heating to complete the preparation of the precursor material;
In the fifth step, the volume of the complexing agent aqueous solution B is 72 percent of the volume of the continuous stirring liquid phase reactor; wherein the volume of the complexing agent aqueous solution B is 720mL, and the volume of the continuous stirring liquid phase reactor is 1L;
in the fifth step, the feeding rate ratio of the four substances fed in the first step is as follows: feeding the mixed metal salt aqueous solution A, the precipitant aqueous solution, the complexing agent aqueous solution A and the fluoride aqueous solution A at a feeding rate ratio of 1:2:1: 1;
Fifthly, the feeding rates of the mixed metal salt water solution B and the mixed metal salt water solution A are the same; the feeding rate of the primary feeding aqueous fluoride solution B is the same as that of the aqueous fluoride solution A;
and sixthly, cooling, namely stirring for 3 hours at the rotating speed of 700r/min to cool the continuous stirring liquid phase reactor to room temperature, thus obtaining the lithium ion battery ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 with low lattice stress.
(I) SEM detection is carried out on the lithium ion battery ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 prepared in the first test, an SEM image of the lithium ion battery ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 shown in the first test shown in figure 1 is obtained, and the average particle size of the precursor is 7-8 mu m, and is spherical secondary particles formed by tightly stacking a large number of flaky primary particles, and the particle size is uniform.
and (II) performing energy spectrum detection on the ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 of the lithium ion battery prepared in the first test to obtain energy spectrum parameters shown in the table 1, wherein the content of the Ni element is reduced from inside to outside, and the content of the F element is reversely changed and increased.
TABLE 1
verification test I:
The excellent performance of the lithium ion battery ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 prepared in the first test in the ternary positive electrode material is detected, and the specific process is as follows:
firstly, cleaning and filtering a ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (OH) 1.925 F 0.075 of the lithium ion battery prepared in the first test to remove soluble impurities in the material, and drying the material in a vacuum atmosphere;
and secondly, pre-burning the dried material obtained in the step one for 8 hours at the temperature of 750 ℃ in an oxygen atmosphere, then mixing the pre-burned material with lithium carbonate according to the molar ratio of 1: 1.05, and sintering for 10 hours at the temperature of 850 ℃ in a pure oxygen atmosphere to obtain gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 powder.
The metal components in the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 are in full-gradient change, the F element is in gradient change along with the metal element, the content x of the Ni element is gradually reduced from inside to outside, and the content n of the F element is in reverse gradient change along with the content x and is gradually increased.
a schematic diagram of the lattice structure comparison of the ternary cathode material before and after gradient fluorine doping in the first verification test is shown in fig. 2; wherein a is a ternary gradient material without gradient F doping, 1 is a part with higher nickel content and has large lattice parameter; 2 is the part with lower nickel content and small lattice parameter; it can be seen from fig. 1 that since the radius of Ni particles is within a certain range, the decrease of the content of Ni element reduces the lattice parameter, and the lattices of the ternary gradient material are not matched, resulting in internal lattice stress. b is a ternary gradient material with low lattice stress, 3 is a part with high nickel content and low fluorine content, 4 is a part with low nickel content and high fluorine content, wherein the content x of Ni and the content n of F are in reverse gradient change, and the increase of F element can increase lattice parameters to make up the reduction of lattice parameters caused by the reduction of Ni content, so that the inner lattice parameters and the outer lattice parameters of the ternary gradient material doped with gradient fluorine are consistent, the lattice is matched, the lattice stress of the prepared oxide anode material is effectively reduced, and the internal stress is small. Therefore, the structural stability of the anode material in the charging and discharging process can be improved, and the cycle performance and the rate capability of the anode material are improved.
And (III) carrying out SEM detection on the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.92 5 F 0.075 prepared in the first verification test to obtain an SEM image of the ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 prepared in the first verification test shown in figure 3, wherein the average particle size of the ternary cathode material is 7-8 mu m, and the ternary cathode material is spherical secondary particles formed by primary particles which are tightly stacked in a granular manner and is uniform in particle size as can be seen from figure 3.
And (IV) carrying out X-ray diffraction detection on the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.92 5 F 0.075 prepared in the first verification test to obtain an XRD (X-ray diffraction) diagram of the ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 prepared in the first verification test shown in figure 4, wherein 1 is the ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared in the first verification test, and the ternary cathode material can be seen from figure 4 to have a standard layered structure and no impurity phase, so that the material disclosed by the invention has a good structure.
And (V) detecting the charge-discharge performance of the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.92 5 F 0.075 prepared in the first verification test to obtain a first charge-discharge curve diagram of the ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 under the multiplying power of 0.1C shown in the first verification test shown in figure 5, wherein the first charge-discharge curve is a typical ternary material charge-discharge curve, the first charge capacity reaches 170mAh g -1, and the first efficiency is 85%, which shows that the material synthesized by the method has high first capacity and high coulombic efficiency.
Sixthly, the rate performance of the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.92 5 F 0.075 prepared in the first verification test is detected, a rate performance curve diagram of the ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 prepared in the first verification test is obtained, and the good rate performance of the gradient fluorine-doped ternary cathode material is shown in FIG. 6.
(VII) cycle performance of the gradient fluorine-doped ternary positive electrode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.92 5 F 0.075 prepared in the first verification test and a control sample gradient ternary positive electrode material LiNi 0.481 Co 0.193 Mn 0.193 O 0.193 under the 1C magnification is detected, and a comparison cycle performance curve diagram of the gradient fluorine-doped ternary positive electrode material LiNi 0.193 Co 0.193 Mn 0.193 F 0.193 prepared in the first verification test and the control sample gradient ternary positive electrode material LiNi 0.193 Co 0.193 Mn 0.193 O 0.193 under the 1C magnification is obtained, wherein 1 is a comparison cycle performance curve diagram of the gradient fluorine-doped ternary positive electrode material LiNi 0.193 Co 0.193 Mn 0.193 O 0.193 F 0.193 prepared in the first verification test, 2 is a comparison sample gradient ternary positive electrode material LiNi 0.193 Co 0.193 Mn 0.193 O 0.193 after the first verification test, and as can be seen from FIG. 7, the gradient fluorine-doped ternary positive electrode material can keep stable in structure due to small lattice stress, the cycle performance is excellent, the cycle performance of the control sample gradient fluorine-doped ternary positive electrode material LiNi 0.193 is excellent in 100 after the cycle performance curve, the cycle performance curve of the control sample gradient 100.100, the cycle performance curve of the control sample is poor after the cycle performance curve of the cycle maintenance ratio of the ternary positive electrode.
(eight) scanning electron microscope detection is carried out on the gradient fluorine-doped gradient ternary cathode material LiNi 0.481 Co 0.193 Mn 0.28 9 O 1.925 F 0.075 prepared in the first verification test and the control gradient ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 2 after circulation for 200 times at the magnification of 1C, and an SEM image of the gradient fluorine-doped ternary cathode material LiNi 0.481 Co 0.193 Mn 0.289 O 1.925 F 0.075 prepared in the first verification test and an SEM image of the control gradient ternary cathode material LiNi 0.481 Co 0.193 Mn 0.193 O 0.193 after circulation for 200 times at the magnification of 1C as shown in FIG. 8 are obtained.
The second test and the preparation method of the lithium ion battery anode precursor material with low lattice stress are carried out according to the following steps:
firstly, preparing a mixed metal salt aqueous solution: mixing nickel sulfate, cobalt sulfate, manganese sulfate and lithium sulfate according to a molar ratio to prepare a mixed metal salt water solution A; the concentration of the mixed metal salt in the mixed metal salt water solution A is 2 mol/L; the molar ratio of the mixed metal salt aqueous solution A is nickel element: cobalt element: manganese element: lithium element 2.7: 0.9: 5.4: 1; mixing nickel sulfate, cobalt sulfate, manganese sulfate and lithium sulfate according to a molar ratio to prepare a mixed metal salt water solution B; the concentration of the mixed metal salt in the mixed metal salt water solution B is 2 mol/L; the molar ratio of the mixed metal salt aqueous solution B is nickel element: cobalt element: manganese element: lithium element 3: 3: 3: 1;
secondly, preparing a precipitant aqueous solution: mixing sodium carbonate with water to prepare a precipitant aqueous solution with the concentration of the sodium carbonate of 2 mol/L;
Thirdly, preparing a complexing agent aqueous solution: firstly, ammonia water is mixed with water to prepare a complexing agent aqueous solution A; the concentration of ammonia water in the complexing agent aqueous solution A is 2.8 mol/L; secondly, mixing ammonia water and water to prepare a complexing agent aqueous solution B; the concentration of ammonia water in the complexing agent aqueous solution B is 0.3 mol/L;
Fourthly, preparing a fluoride aqueous solution: firstly, mixing ammonium fluoride with water to prepare a fluoride aqueous solution A; the concentration of ammonium fluoride in the fluoride aqueous solution A is 0.01 mol/L; secondly, mixing ammonium fluoride with water to prepare a fluoride water solution B; the concentration of ammonium fluoride in the fluoride aqueous solution B is 0.15 mol/L;
fifthly, preparing a precursor material: adding the water solution B of the complexing agent in the third step into a continuous stirring liquid phase reactor to be used as reaction base liquid, and then carrying out the following steps of: respectively and continuously injecting a mixed metal saline solution A, a precipitator aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as primary feeding materials under the conditions of inert atmosphere, pH value of 10 +/-0.3, constant temperature of 60 ℃ and rotation speed of 900r/min, respectively injecting a mixed metal saline solution B and a fluoride aqueous solution B into a mixed metal saline solution A and a fluoride aqueous solution A as secondary feeding materials while injecting the primary feeding materials, respectively and continuously injecting the mixed metal saline solution B and the fluoride aqueous solution B into the whole preparation process, regulating the rotation speed from 900r/min to 300r/min after the reaction is carried out for 1h, reacting for 2h at the regulated rotation speed, opening an overflow pipe to start overflowing, wherein the overflowing amount is the feeding amount within 2h in the step III, and recovering the amount of the solution in the continuous stirring liquid phase reactor to the solution amount at the starting time in the step III, fifthly, repeating the step IV until the total reaction time is 12 hours, stopping adding the primary feeding and the secondary feeding at the moment, and stopping heating to complete the preparation of the precursor material;
In the fifth step, the volume of the complexing agent aqueous solution B is 72 percent of the volume of the continuous stirring liquid phase reactor; wherein the volume of the complexing agent aqueous solution B is 720mL, and the volume of the continuous stirring liquid phase reactor is 1L;
in the fifth step, the feeding rate ratio of the four substances fed in the first step is as follows: feeding the mixed metal salt aqueous solution A, the precipitant aqueous solution, the complexing agent aqueous solution A and the fluoride aqueous solution A at a feeding rate ratio of 1:1:1: 1;
fifthly, the feeding rates of the mixed metal salt water solution B and the mixed metal salt water solution A are the same; the feeding rate of the primary feeding aqueous fluoride solution B is the same as that of the aqueous fluoride solution A;
And sixthly, cooling, namely stirring for 3 hours at the rotating speed of 700r/min to reduce the temperature of the continuous stirring liquid phase reactor to room temperature, thus obtaining the ternary positive electrode precursor material Ni 0.481 Co 0.193 Mn 0.289 Li 0.075 (CO 3) 0.9625 F 0.075 with low lattice stress.
The difference between the third test and the first test is as follows: in the second step, the precipitator is a mixture of sodium hydroxide and lithium hydroxide, wherein the molar ratio of the sodium hydroxide to the lithium hydroxide is 1: 1.
the fourth test and the first test are different in that: and in the third step, the complexing agent is a mixture of ammonia water and ammonium chloride, wherein the molar ratio of the ammonia water to the ammonium chloride is 1: and M is a mixture of magnesium and aluminum and exists in the forms of magnesium sulfate and aluminum sulfate respectively, wherein the molar ratio of the magnesium sulfate to the aluminum sulfate is 1: 1.
The difference between the fifth test and the first test is as follows: the fluoride in the fourth step is a mixture of sodium fluoride and ammonium fluoride, wherein the molar ratio of the sodium fluoride to the ammonium fluoride is 1: 1.
The difference between the sixth test and the first test is as follows: step one, the molar ratio of the mixed metal salt aqueous solution A is nickel: cobalt: manganese: the molar ratio of Li element is 7.2: 0.9: 0.9: 1.
the seventh test is different from the first test in that: the total reaction time in the fifth step is 16 h.
the difference between the eighth test and the first test is as follows: the pH value of the reaction in the fifth step is set to be 10.7 +/-0.3.
the difference between the ninth test and the first test is as follows: in the third step, the concentration of ammonia water in the complexing agent aqueous solution A is 0.6mol/L, in the first step, M is a mixture of calcium and magnesium, and the ammonia water and the magnesium exist in the forms of calcium nitrate and magnesium sulfate respectively, wherein the molar ratio of the calcium nitrate to the magnesium sulfate is 1: 1.
the difference between the tenth test and the first test is as follows: the nickel salt is nickel chloride, the cobalt salt is cobalt chloride, and the manganese salt is manganese chloride.
Claims (6)
1. a preparation method of a lithium ion battery anode precursor material with low lattice stress is characterized in that the preparation method of the lithium ion battery anode precursor material with low lattice stress is carried out according to the following steps:
1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 2firstly, mixing nickel salt, cobalt salt, manganese salt and M salt according to a molar ratio to prepare a mixed metal brine solution A, wherein the concentration of the mixed metal salt in the mixed metal brine solution A is 0.01-20 mol/L, the molar ratio of nickel element to cobalt element to manganese element to M element is x: y: z (1-x-y-z), wherein x is not less than 0 and not more than 1, y is not less than 0 and not more than 1, z is not less than 0 and not more than 1, x + y + z is not more than 0 and not more than 1, mixing nickel salt, cobalt salt, manganese salt and M salt according to a molar ratio to prepare a mixed metal brine solution B, the concentration of the mixed metal salt in the mixed metal brine solution B is 0.01-20 mol/L, the molar ratio of nickel element to manganese element to M element is not less than x: y: z (1-x-y-z), wherein x is not more than 0 and not more than 1, y is not more than 0 and not more than 1, and z is not more than 1 when x-z is not more than 1 and x-y-z;
the M salt is one or a mixture of more of soluble sulfate, soluble nitrate, soluble acetate, soluble chloride, soluble citrate and soluble alkoxide; wherein M is one or a mixture of more of Li, Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi;
Secondly, preparing a precipitant aqueous solution: mixing a precipitator with water to prepare a precipitator aqueous solution with the concentration of 0.01-20 mol/L;
thirdly, preparing a complexing agent aqueous solution: mixing a complexing agent with water to prepare a complexing agent aqueous solution A; the concentration of the complexing agent in the complexing agent aqueous solution A is 0.01-20 mol/L; mixing complexing agent with water to prepare complexing agent water solution B; the concentration of the complexing agent in the complexing agent water solution B is 0.01-10 mol/L;
Fourthly, preparing a fluoride aqueous solution: mixing fluoride with water to prepare a fluoride aqueous solution A; the concentration of fluoride in the fluoride aqueous solution A is 0.001 mol/L-2 mol/L; ② mixing fluoride with water to prepare a fluoride water solution B; the concentration of the fluoride in the fluoride aqueous solution B is 0-2 mol/L;
Fifthly, preparing a precursor material: adding the water solution B of the complexing agent in the third step into a continuous stirring liquid phase reactor to be used as reaction base liquid, and then carrying out the following steps of: respectively and continuously injecting a mixed metal salt aqueous solution A, a precipitant aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as primary feeding materials under the conditions of inert atmosphere, pH value of 4-14, constant temperature of 10-85 ℃ and rotation speed of 600-1000 r/min, respectively injecting a mixed metal salt aqueous solution A, a precipitant aqueous solution, a complexing agent aqueous solution A and a fluoride aqueous solution A into a continuous stirring liquid phase reactor as secondary feeding materials while injecting the primary feeding materials, respectively and continuously injecting a mixed metal salt aqueous solution B and a fluoride aqueous solution B into the mixed metal salt aqueous solution A and the fluoride aqueous solution A, wherein the primary feeding materials and the secondary feeding materials are added continuously for the whole preparation process, when the reaction is carried out until the solid-liquid mass ratio in the continuous stirring liquid phase reactor is 1/40-1/5, the rotation speed is adjusted from 600 r/min-1000 r/min, the adjustment range is 200r/, opening an overflow pipe to overflow, wherein the overflow amount is the feeding amount in the time of the step (III), so that the amount of the solution in the continuous stirring liquid phase reactor is recovered to the amount of the solution at the starting moment of the step (III), repeating the step (IV) until the total reaction time is 5-30 h, stopping the addition of the primary feeding and the secondary feeding at the moment, and stopping heating to finish the preparation of the precursor material;
in the fifth step, the volume of the complexing agent aqueous solution B is 10-80% of the volume of the continuous stirring liquid phase reactor;
feeding rate ratios of the four substances of the primary feed in the fifth step are that when the chemical formula of the precursor material is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n, the feeding rate ratio of the mixed metal saline solution A to the precipitant aqueous solution to the complexing agent aqueous solution A to the fluoride aqueous solution A is 1:2:1:1, and when the chemical formula of the precursor material is Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n, the feeding rate ratio of the mixed metal saline solution A to the precipitant aqueous solution to the complexing agent aqueous solution A to the fluoride aqueous solution A is 1:1:1: 1;
fifthly, the feeding rates of the mixed metal salt water solution B and the mixed metal salt water solution A are the same; the feeding rate of the primary feeding aqueous fluoride solution B is the same as that of the aqueous fluoride solution A;
In the fifth step, the ratio of the total moles of the complexing agent in the complexing agent aqueous solution A, B to the total moles of the metal salt in the mixed metal salt aqueous solution A, B is 0.1-10.0: 1; the ratio of the mole number of the precipitant in the precipitant aqueous solution to the total mole number of the metal salt in the mixed metal salt aqueous solution A, B is 0.1-4.0: 1; the ratio of the total moles of fluoride in the aqueous fluoride solution A, B to the total moles of metal salts in the aqueous mixed metal salt solution A, B is 0.001-2.0: 1;
sixthly, cooling, namely stirring for 1-3 h under the condition that the rotating speed is 500-1000 r/min to reduce the temperature of the continuously stirred liquid phase reactor to room temperature, thus obtaining the lithium ion battery anode precursor material Ni x Co y Mn z M 1-x-y-z (OH) 2- n F n or Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n with low lattice stress.
2. The method for preparing the lithium ion battery anode precursor material with low lattice stress according to claim 1, wherein the nickel salt in the step one is one or a mixture of several of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride; the cobalt salt is one or a mixture of more of cobalt sulfate, cobalt nitrate, cobalt acetate and cobalt chloride; the manganese salt is one or a mixture of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.
3. the method for preparing the lithium ion battery positive electrode precursor material with low lattice stress according to claim 1, wherein in the second step, when the precursor material is Ni x Co y Mn z M 1-x-y-z (OH) 2-n F n, one or a mixture of several of sodium hydroxide, potassium hydroxide and lithium hydroxide is used as the precipitant.
4. The method for preparing the lithium ion battery positive electrode precursor material with low lattice stress according to claim 1, wherein the precipitating agent is one or a mixture of sodium carbonate, potassium carbonate and lithium carbonate when the precursor material in the second step is Ni x Co y Mn z M 1-x-y-z (CO 3) 1-0.5n F n.
5. the method for preparing the lithium ion battery positive electrode precursor material with low lattice stress according to claim 1, wherein the complexing agent in step three is one or a mixture of more of ammonia water, ammonium chloride, ammonium fluoride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid and malonic acid.
6. the method for preparing the precursor material of the lithium ion battery positive electrode with low lattice stress according to claim 1, wherein the fluoride in the fourth step is one or a mixture of sodium fluoride, potassium fluoride and ammonium chloride.
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