CN112408503A - Fluorinated high-nickel ternary material and preparation method and application thereof - Google Patents
Fluorinated high-nickel ternary material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrode materials, in particular to a fluorinated high-nickel ternary material and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: performing vacuum rectification on the electrolyte of the failed lithium ion battery, and crystallizing the obtained residual liquid by using ammonia water to obtain lithium fluoride; mixing lithium fluoride, nickel sulfate, cobalt sulfate, manganese sulfate and water to obtain a mixed solution; mixing the mixed solution with a complexing agent, and aging to obtain a precursor; and mixing the precursor with lithium hydroxide, and calcining to obtain the fluorinated high-nickel ternary material. The fluorinated high-nickel ternary material prepared by the preparation method has good circulation stability and high-rate charge and discharge performance.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a fluorinated high-nickel ternary material and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used because of their excellent properties, such as high voltage, high capacity, high cycle and good thermal stability. With the development of technology, lithium cobaltate is subject to structural stability and price, and the position of lithium cobaltate will be replaced by other materials in the future. The layered nickel-cobalt-manganese ternary material has the advantages of high specific capacity, good safety performance, low production cost and the like, has steadily increased position in the lithium battery industry, and is considered to be the most promising lithium cobaltate-replacing lithium battery positive electrode material at present. However, with the rapid development of modern technologies, people have increasingly high performance requirements for lithium batteries, such as pursuit of high energy density, high voltage, and the like. Therefore, people put great research and development efforts on the high-nickel ternary materials (NCM and NCA), the high-nickel precursor is also important for research and development as the matrix precursor of the high-nickel ternary materials, and the crystallization synthesis conditions of the nickel source, the cobalt source and the manganese source of the high-nickel precursor are very harsh, so that the nickel source is easily lost in a large amount, and the effective nickel-cobalt-manganese crystal cannot be completely synthesized.
In order to solve the above problems, modification studies are mainly conducted on the molded ternary material at the present stage, but the effect of improving the performance is still very small. Although the capacity of the ternary material of the lithium battery can be maximized under high voltage, with the increase of the cycle times, the interface differentiation of primary particles or the separation of agglomerated single crystals may occur at the later stage of secondary particles or the agglomerated single crystals, the internal resistance becomes large, the battery capacity is rapidly attenuated, and the cycle performance becomes poor.
Disclosure of Invention
The invention aims to provide a fluorinated high-nickel ternary material and a preparation method and application thereof. The fluorinated high-nickel ternary material prepared by the preparation method has good circulation stability and high-rate charge and discharge performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a fluorinated high-nickel ternary material, which comprises the following steps:
performing vacuum rectification on the electrolyte of the failed lithium ion battery, and crystallizing the obtained residual liquid by using ammonia water to obtain lithium fluoride;
mixing the lithium fluoride, nickel sulfate, cobalt sulfate, manganese sulfate and water to obtain a mixed solution;
mixing the mixed solution with a complexing agent, and aging to obtain a precursor; the chemical formula of the precursor is NixCoyMnz(OH)2nLiF, wherein x is not less than 0.5, and x + y + z is 1; n is 0.05 to 0.5;
and mixing the precursor with lithium hydroxide, and calcining to obtain the fluorinated high-nickel ternary material.
Preferably, the temperature of the vacuum rectification is 95-120 ℃.
Preferably, the ratio of the total amount of the cobalt in the cobalt sulfate and the manganese in the manganese sulfate to the amount of the nickel in the nickel sulfate is (0-0.5): (0.5-1), wherein the total amount of the cobalt in the cobalt sulfate and the manganese in the manganese sulfate is not 0;
the ratio of the total amount of nickel in the nickel sulfate, cobalt in the cobalt sulfate and manganese in the manganese sulfate to the amount of lithium in the lithium fluoride is 1: (0.05-0.5).
Preferably, the total concentration of solutes in the mixed solution is 1.5-2 mol/L.
Preferably, the complexing agent is ammonia water;
the concentration of the ammonia water is 2-3 mol/L;
the aging time is 10-12 h, and the ammonia content in the mixed liquid is kept at 10 +/-0.5 g/L in the aging process.
Preferably, after the mixed solution and the complexing agent are mixed, the pH value of the obtained mixed solution is adjusted;
the regulator used for regulating the pH value is a NaOH solution with the concentration of 1-2 mol/L;
and adjusting the pH value to obtain the pH value of the liquid to be aged which is 11-12.
Preferably, the molar ratio of the precursor to the lithium hydroxide is 1: (1.05-1.2).
Preferably, the calcination comprises a first calcination step, a second calcination step and a third calcination step which are sequentially carried out;
the temperature of the first step of calcination is 400 ℃, and the time is 2 hours;
the temperature of the second step of calcination is 650 ℃, and the time is 8 hours;
the temperature of the third step of calcination is 800 ℃, and the time is 10 h.
The invention also provides a fluorinated high-nickel ternary material prepared by the preparation method of the technical scheme, and the chemical formula of the fluorinated high-nickel ternary material is LimNixCoyMnzO2·nF；
Wherein x is more than or equal to 0.5, and x + y + z is 1; m is 1.05 to 1.25; n is 0.05 to 0.5.
The invention also provides the application of the fluorinated high-nickel ternary material in the technical scheme in the field of lithium ion batteries.
The invention provides a preparation method of a fluorinated high-nickel ternary material, which comprises the following steps: performing vacuum rectification on the electrolyte of the failed lithium ion battery, and crystallizing the obtained residual liquid by using ammonia water to obtain lithium fluoride; mixing lithium fluoride, nickel sulfate, cobalt sulfate, manganese sulfate and water to obtain a mixed solution; mixing the mixed solution with a complexing agent, and aging to obtain a precursor; the chemical formula of the precursor is NixCoyMnz(OH)2nLiF, wherein x is not less than 0.5, and x + y + z is 1; n is 0.05 to 0.5; and mixing the precursor with lithium hydroxide, and calcining to obtain the fluorinated high-nickel ternary material.
Compared with the prior art, the preparation method has the following beneficial effects:
1) after the aged lithium ion battery electrolyte is subjected to vacuum rectification treatment, lithium fluoride with higher purity can be obtained, so that the method is economic and environment-friendly;
2) the precursor prepared by the preparation method provided by the invention is prepared by taking lithium fluoride as a matrix material for crystallization and wrapping, so that Ni, Co and Mn have uniform adhesive force during precipitation, are dispersed more uniformly and have more complete crystallinity;
3) the matrix material lithium fluoride not only achieves the effect of providing a lithium source but also achieves the effect of fluxing in the subsequent calcining process, so that in the calcining process, the lithium fluoride crystal inside and the nickel, cobalt and manganese hydroxide coated outside the lithium fluoride crystal are fully oxidized, the crystal form is more stable and is not easy to pulverize;
4) the fluorinated high-nickel ternary material has the characteristics of improving the transfer efficiency of lithium ions and being difficult to crush material crystals under high voltage in the charge and discharge processes of a battery, and further has higher cycle stability and high-rate charge and discharge performance;
according to the description of the embodiment, the lithium ion battery prepared by using the fluorinated high-nickel ternary material prepared by the preparation method provided by the invention as an electrode material of the lithium ion battery has the capacity retention rate of about 96% after 300 cycles of charge-discharge cycle under the current density of 0.5C, and simultaneously has good rate capability.
Drawings
FIG. 1 is an SEM image of a precursor and a fluorinated high-nickel ternary material prepared in example 1;
FIG. 2 is a charge-discharge cycle diagram at 0.5C for a battery prepared from the fluorinated high-nickel ternary material described in examples 1-4;
FIG. 3 is a plot of the percent discharge capacity of the fluorinated high nickel ternary material of example1 at 0.2C, 0.5C, and 1C, respectively;
FIG. 4 is an XRD pattern of the fluorinated nickel-rich ternary material according to examples 1-4.
Detailed Description
The invention provides a preparation method of a fluorinated high-nickel ternary material, which comprises the following steps:
performing vacuum rectification on the electrolyte of the failed lithium ion battery, and crystallizing the obtained residual liquid by using ammonia water to obtain lithium fluoride;
mixing lithium fluoride, nickel sulfate, cobalt sulfate, manganese sulfate and water to obtain a mixed solution;
mixing the mixed solution with a complexing agent, and aging to obtain a precursor; the chemical formula of the precursor is NixCoyMnz(OH)2nLiF, wherein x is not less than 0.5, and x + y + z is 1; n is 0.05 to 0.5;
and mixing the precursor with lithium hydroxide, and calcining to obtain the fluorinated high-nickel ternary material.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of performing vacuum rectification on the electrolyte of the failed lithium ion battery, and crystallizing the obtained residual liquid by using ammonia water to obtain the lithium fluoride.
The invention does not have any special limitation on the types of the aged lithium ion battery electrolyte, and the aged lithium ion battery electrolyte can be prepared by adopting the existing organic electrolyte used in the lithium ion battery and well known to the technical personnel in the field.
In the invention, the purpose of the vacuum rectification is to distill off the carbonate organic solvent in the aged lithium ion battery electrolyte and obtain a residual liquid containing lithium fluoride; and the carbonate organic solvent is recycled, and the residual liquid containing the lithium fluoride is used for the subsequent process of preparing the fluorinated high-nickel ternary material.
In the invention, the temperature of the vacuum rectification is preferably 95-120 ℃, more preferably 98-105 ℃, and most preferably 100-102 ℃; the vacuum degree of the vacuum rectification is preferably 0.1-2 KPa. The vacuum rectification time is not limited at all, and the titanate organic solvent in the failure lithium ion battery electrolyte can be ensured to be completely distilled out.
In the present invention, the crystallization process of the obtained raffinate with ammonia water is preferably as follows: and flushing the residual liquid by using ammonia water. In the invention, the concentration of the ammonia water is preferably 1.5-2 mol/L, and more preferably 1.6-1.8 mol/L; in the invention, the washing temperature is preferably 60-75 ℃, and more preferably 65-70 ℃; the washing frequency is preferably 4-6 times, and more preferably 5 times; the invention has no special limit on the dosage of the ammonia water during each flushing, and ensures that no new lithium fluoride crystal exists.
After the lithium fluoride is obtained, the lithium fluoride, nickel sulfate, cobalt sulfate, manganese sulfate and water are mixed to obtain a mixed solution. In the present invention, the nickel sulfate is preferably NiSO4·6H2O; the cobalt sulfate is preferably CoSO4·7H2And O. In the invention, the ratio of the total amount of the cobalt in the cobalt sulfate and the manganese in the manganese sulfate to the amount of the nickel in the nickel sulfate is preferably (0-0.5): (0.5 to 1), more preferably (0.1 to 0.4): (0.6-0.9), most preferably (0.2-0.3): (0.7-0.8). In the present embodiment, the ratio of the amounts of cobalt in the cobalt sulfate to manganese in the manganese sulfate is preferably (0.1 to 0.25): (0.1 to 0.3), more preferably (0.2 to 0.25): (0.2-0.3). In the invention, the total concentration of the solute in the mixed solution is preferably 1.5-2 mol/L, more preferably 1.6-1.9 mol/L, and most preferably 1.7-1.8 mol/L. The mixing process is not particularly limited, and may be performed by a method known to those skilled in the art.
After a mixed solution is obtained, the mixed solution and a complexing agent are mixed and aged to obtain a precursor; the chemical formula of the precursor is NixCoyMnz(OH)2nLiF, wherein x is not less than 0.5, and x + y + z is 1; n is 0.05 to 0.5. In the invention, the ratio of y to z in the precursor is preferably (0.1-0.25): (0.1 to 0.3), more preferably (0.2 to 0.25): (0.2-0.3). In the invention, the complexing agent is preferably ammonia water, and the concentration of the ammonia water is preferably 2-3 mol/L, more preferably 2.2-2.8 mol/L, and most preferably 2.4-2.6 mol/L.
In the invention, the mixing temperature is preferably 45-70 ℃, and more preferably 55-60 ℃; the mixing is preferably carried out under stirring, preferably at a rate of 300 r/min.
After the mixing is finished, the invention also preferably comprises the step of adjusting the pH value of the obtained mixed solution; the regulator used for regulating the pH value is a NaOH solution with the concentration of 1-2 mol/L; and adjusting the pH value to obtain the pH value of the liquid to be aged which is 11-12.
In the invention, the addition of the complexing agent can enable cations of nickel, cobalt and manganese to form a stable and uniform complex, and adjust the pH to react with hydroxyl so as to obtain a precursor with better quality.
In the invention, after the above process is completed, nickel-cobalt-manganese can be completely and uniformly deposited on the surface of lithium fluoride in the form of hydroxide.
In the invention, the aging temperature is preferably 45-70 ℃, and more preferably 50-65 ℃; the aging time is preferably 10-12 h, and more preferably 11 h. In the present invention, it is preferable to keep the ammonia content in the mixed solution at 10. + -. 0.5g/L during the aging.
After the aging is finished, the invention also preferably comprises filtering, washing and drying which are carried out in sequence; the filtration is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art. In the invention, the washing times are preferably 3-4 times; in the present invention, the drying is preferably microwave drying; the conditions for the microwave drying in the present invention are not particularly limited, and may be those well known to those skilled in the art.
After the drying is finished, the invention also preferably comprises the steps of sequentially screening and deironing the product obtained after the drying; the screening is preferably multi-layer screening to 325 mesh. The iron removal process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
After the precursor is obtained, the precursor and lithium hydroxide are mixed and calcined to obtain the fluorinated high-nickel ternary material. In the present invention, the molar ratio of the precursor to lithium hydroxide is preferably 1: (1.05 to 1.2), more preferably 1: (1.10-1.15). The mixing is not particularly limited in the present invention and may be carried out by a procedure well known to those skilled in the art.
In the present invention, the calcination preferably includes a first calcination, a second calcination, and a third calcination, which are performed in this order; the temperature of the first-step calcination is preferably 400 ℃, and the time is preferably 2 h; the temperature of the second step of calcination is preferably 650 ℃, and the time is preferably 8 h; the temperature of the third step of calcination is preferably 800 ℃ and the time is preferably 10 h.
In the invention, the first step of calcination can combine the mixed lithium salt and the precursor under the action of more effective thermal stress, and reduce the loss of the lithium salt; the second step of calcination can accelerate crystal growth and solid-phase binding reaction; and the third step of calcination ensures that the crystal structure of the generated high nickel fluoride ternary material tends to be more complete and stable, and the internal lithium fluoride can also have the effects of lithium supplement and fluxing when the temperature reaches 800 ℃.
After the calcination is finished, the invention also preferably comprises the steps of sequentially grinding, deironing and screening the calcined material. The process of grinding, iron removal and screening is not particularly limited in the present invention and may be performed by a process well known to those skilled in the art. In the present invention, the screened rejects are preferably 325 mesh.
The invention also provides a fluorinated high-nickel ternary material prepared by the preparation method of the technical scheme, and the chemical formula of the fluorinated high-nickel ternary material is LimNixCoyMnzO2·nF；
Wherein x is more than or equal to 0.5, and x + y + z is 1; m is 1.05 to 1.25; n is 0.05 to 0.5.
In the invention, the ratio of y to z is preferably (0.1-0.25): (0.1 to 0.3), more preferably (0.2 to 0.25): (0.2-0.3).
The invention also provides the application of the fluorinated high-nickel ternary material in the technical scheme in the field of lithium ion batteries. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The fluorinated nickelic ternary material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example1
After the failed lithium ion battery electrolyte is subjected to vacuum rectification (the vacuum degree is 1KPa, and the temperature is 115 ℃), controlling the temperature to be 65 ℃, and washing the obtained residual liquid for multiple times by adopting ammonia water with the concentration of 1.5mol/L to crystallize to obtain lithium fluoride;
adding lithium fluoride and NiSO4·6H2O、CoSO4·7H2Mixing O, manganese sulfate and water to obtain a mixed solution, wherein the molar ratio of Ni, Co and Mn is 8:1:1, the molar ratio of Li to the total molar ratio of Ni, Co and Mn is 0.05:1, and the total concentration of solutes in the mixed solution is 2 mol/L;
adding 2mol/L ammonia water into the mixed solution at the temperature of 60 ℃ and the stirring speed of 320r/min, adjusting the pH value to 12 by using 1.5mol/L NaOH solution, aging for 11h after nickel, cobalt and manganese are completely deposited on the surface of lithium fluoride, sequentially filtering, washing for 3-4 times, performing microwave drying, and finally performing 325-mesh screening and iron removal to obtain a precursor (Ni)0.8Co0.1Mn0.1(OH)2·0.05LiF)；
Mixing the precursor and LiOH according to a molar ratio of 1:1.05, and then carrying out three-step calcination: 400 ℃ for 2 h; cooling at 650 ℃, 8h and 800 ℃ for 10h, grinding and deironing the material obtained after cooling in sequence, and sieving with a 325-mesh sieve to obtain the nickel fluoride ternary material (Li)1.1Ni0.8Co0.1Mn0.1O2·0.05F)；
Adding the Ni0.8Co0.1Mn0.1(OH)20.05LiF and Li1.1Ni0.8Co0.1Mn0.1O20.05F, as shown in FIG. 1, the result of SEM test is that the doping of fluorine can significantly improve the crystal structure of the particles, so that Ni is added0.8Co0.1Mn0.1(OH)2The single crystal form is combined more tightly, can inhibit the material from generating lattice distortion in the cyclic charge-discharge process, and increases the primary particle size of the material, thereby ensuring that the material has stability under high voltage and stabilityPulverization of uniform single crystal particles with effective reduction of Li+The SEI film is more effectively formed and the generation of lithium dendrite is inhibited by the times of passing through the crystal boundary in the de-intercalation process.
Example2
After the spent lithium ion battery electrolyte is subjected to vacuum rectification (the vacuum degree is 0.8KPa, and the temperature is 115 ℃), controlling the temperature to be 60 ℃, and washing the obtained residual liquid for multiple times by adopting ammonia water with the concentration of 1.5mol/L to crystallize to obtain lithium fluoride;
adding lithium fluoride and NiSO4·6H2O、CoSO4·7H2Mixing O, manganese sulfate and water to obtain a mixed solution, wherein the molar ratio of Ni, Co and Mn is 8:1:1, the molar ratio of Li to the total molar ratio of Ni, Co and Mn is 0.1:1, and the total concentration of solutes in the mixed solution is 1.8 mol/L;
adding 2mol/L ammonia water into the mixed solution at 55 ℃ and at a stirring speed of 300r/min to keep the concentration of the ammonia in a subsequent aging system at 10 +/-0.5 g/L, adjusting the pH value to 11.5 by using 1.5mol/L NaOH solution, aging for 10h after the nickel, cobalt and manganese are completely deposited on the surface of lithium fluoride, sequentially filtering, washing for 3-4 times and microwave drying, and finally carrying out 325-mesh screening and iron removal to obtain a precursor (Ni)0.8Co0.1Mn0.1(OH)2·0.1LiF)；
Mixing the precursor and LiOH according to a molar ratio of 1:1.05, and then carrying out three-step calcination: 400 ℃ for 2 h; cooling at 650 ℃, 8h and 800 ℃ for 10h, grinding and deironing the material obtained after cooling in sequence, and sieving with a 325-mesh sieve to obtain the nickel fluoride ternary material (Li)1.15Ni0.8Co0.1Mn0.1O2·0.1F)。
Example3
After the failed lithium ion battery electrolyte is subjected to vacuum rectification (the vacuum degree is 1.2KPa, and the temperature is 100 ℃), controlling the temperature to be 65 ℃, and washing the obtained residual liquid for multiple times by adopting ammonia water with the concentration of 1.5mol/L to crystallize to obtain lithium fluoride;
adding lithium fluoride and NiSO4·6H2O、CoSO4·7H2Mixing O, manganese sulfate and water to obtain a mixed solution, wherein the molar ratio of Ni, Co and Mn is 8:1:1, the molar ratio of Li to the total molar ratio of Ni, Co and Mn is 0.15:1, and the total concentration of solutes in the mixed solution is 2 mol/L;
adding 2mol/L ammonia water into the mixed solution at the temperature of 60 ℃ and the stirring speed of 320r/min to keep the concentration of the ammonia in a subsequent aging system at 10 +/-0.5 g/L, adjusting the pH value to 12 by using 1.5mol/L NaOH solution, aging for 11h after the nickel, cobalt and manganese are completely deposited on the surface of lithium fluoride, sequentially filtering, washing for 3-4 times and microwave drying, and finally screening for 325 meshes and removing iron to obtain a precursor (Ni) to obtain the precursor (Ni0.8Co0.1Mn0.1(OH)2·0.15LiF)；
Mixing the precursor and LiOH according to a molar ratio of 1:1.05, and then carrying out three-step calcination: 400 ℃ for 2 h; cooling at 650 ℃, 8h and 800 ℃ for 10h, grinding and deironing the material obtained after cooling in sequence, and sieving with a 325-mesh sieve to obtain the nickel fluoride ternary material (Li)1.2Ni0.8Co0.1Mn0.1O2·0.15F)。
Example4
After the failed lithium ion battery electrolyte is subjected to vacuum rectification (the vacuum degree is 0.5KPa, and the temperature is 95 ℃), controlling the temperature to be 60 ℃, and washing the obtained residual liquid for multiple times by adopting ammonia water with the concentration of 1.5mol/L to crystallize to obtain lithium fluoride;
adding lithium fluoride and NiSO4·6H2O、CoSO4·7H2Mixing O, manganese sulfate and water to obtain a mixed solution, wherein the molar ratio of Ni, Co and Mn is 8:1:1, the molar ratio of Li to the total molar ratio of Ni, Co and Mn is 0.2:1, and the total concentration of solutes in the mixed solution is 1.7 mol/L;
adding 2mol/L ammonia water into the mixed solution at the temperature of 60 ℃ and the stirring speed of 320r/min to keep the concentration of the ammonia in a subsequent aging system at 10 +/-0.5 g/L, adjusting the pH value to 12 by using 1.5mol/L NaOH solution, aging for 11h after the nickel, cobalt and manganese are completely deposited on the surface of the lithium fluoride, sequentially filtering, washing for 3-4 times and microwave drying, and finally performing 3 times of microwave dryingSieving with 25 mesh sieve and removing iron to obtain precursor (Ni)0.8Co0.1Mn0.1(OH)2·0.2LiF)；
Mixing the precursor and LiOH according to a molar ratio of 1:1.05, and then carrying out three-step calcination: 400 ℃ for 2 h; cooling at 650 ℃, 8h and 800 ℃ for 10h, grinding and deironing the material obtained after cooling in sequence, and sieving with a 325-mesh sieve to obtain the nickel fluoride ternary material (Li)1.25Ni0.8Co0.1Mn0.1O2·0.2F)。
Test example
Preparing the fluorinated high-nickel ternary material described in the embodiment 1-4 into a button cell, wherein a diaphragm of the button cell is Polyethylene (PE), and an electrolyte is Ethylene Carbonate (EC): the volume ratio of dimethyl carbonate (DMC) is 1:1. LiPF6The positive electrode is the fluorinated high nickel ternary material described in the embodiments 1-4, and the negative electrode is graphite; the mass ratio of the fluorinated high-nickel ternary material to the binder (PVDF) to the conductive agent (acetylene black) is 0.96:0.02: 0.02.
Fig. 2 is a normal-temperature cycle performance diagram of batteries prepared from the fluorinated high-nickel ternary material in examples 1 to 4 at a current density of 0.5C, and as can be seen from fig. 2, the capacity retention rate of the batteries prepared from the fluorinated high-nickel ternary material in example1 after 300 cycles is 97.2%, in example2 is 96.8%, in example3 is 96.9%, and in example4 is 96.4%;
fig. 3 is a discharge capacity percentage curve of the fluorinated high-nickel ternary material in example1 at 0.2C, 0.5C, and 1C, respectively, and it can be seen from fig. 3 that the discharge efficiencies of the fluorinated high-nickel ternary material prepared in example1 at 0.2C, 0.5C, and 1C are 99%, 97%, and 95%, respectively; thus showing the stability and high-rate charge-discharge performance of the fluorinated ternary material under high rate.
XRD (X-ray diffraction) tests are carried out on the nickel fluoride ternary materials in the embodiments 1-4, and the test results are shown in FIG. 4 (wherein example1 corresponds to the embodiment 1, example2 corresponds to the embodiment 2, example3 corresponds to the embodiment 3, and example4 corresponds to the embodiment 4), and as can be seen from FIG. 4, the nickel fluoride ternary materials prepared in the embodiments 1-4 have high crystallinity and are free of impurity phases; in the examples, the crystal form is not changed when the amount of the doped fluorine element is continuously increased.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a fluorinated high-nickel ternary material is characterized by comprising the following steps:
performing vacuum rectification on the electrolyte of the failed lithium ion battery, and crystallizing the obtained residual liquid by using ammonia water to obtain lithium fluoride;
mixing the lithium fluoride, nickel sulfate, cobalt sulfate, manganese sulfate and water to obtain a mixed solution;
mixing the mixed solution with a complexing agent, and aging to obtain a precursor; the chemical formula of the precursor is NixCoyMnz(OH)2nLiF, wherein x is not less than 0.5, and x + y + z is 1; n is 0.05 to 0.5;
and mixing the precursor with lithium hydroxide, and calcining to obtain the fluorinated high-nickel ternary material.
2. The method of claim 1, wherein the vacuum distillation temperature is 95-120 ℃.
3. The method according to claim 1, wherein the ratio of the total amount of the cobalt in the cobalt sulfate and the manganese in the manganese sulfate to the amount of the nickel in the nickel sulfate is (0-0.5): (0.5-1), wherein the total amount of the cobalt in the cobalt sulfate and the manganese in the manganese sulfate is not 0;
the ratio of the total amount of nickel in the nickel sulfate, cobalt in the cobalt sulfate and manganese in the manganese sulfate to the amount of lithium in the lithium fluoride is 1: (0.05-0.5).
4. The method according to claim 1 or 3, wherein the total concentration of the solute in the mixed solution is 1.5 to 2 mol/L.
5. The method of claim 1, wherein the complexing agent is ammonia;
the concentration of the ammonia water is 2-3 mol/L;
the aging time is 10-12 h, and the ammonia content in the mixed liquid is kept at 10 +/-0.5 g/L in the aging process.
6. The method according to claim 1 or 5, wherein after the mixing of the mixed solution and the complexing agent, further comprising the step of adjusting the pH of the obtained mixed solution;
the regulator used for regulating the pH value is a NaOH solution with the concentration of 1-2 mol/L;
and adjusting the pH value to obtain the pH value of the liquid to be aged which is 11-12.
7. The method according to claim 1, wherein the molar ratio of the precursor to lithium hydroxide is 1: (1.05-1.2).
8. The method according to claim 1, wherein the calcination comprises a first calcination step, a second calcination step and a third calcination step, which are performed in this order;
the temperature of the first step of calcination is 400 ℃, and the time is 2 hours;
the temperature of the second step of calcination is 650 ℃, and the time is 8 hours;
the temperature of the third step of calcination is 800 ℃, and the time is 10 h.
9. The fluorinated high-nickel ternary material prepared by the preparation method of any one of claims 1 to 8, wherein the chemical formula of the fluorinated high-nickel ternary material is LimNixCoyMnzO2·nF；
Wherein x is more than or equal to 0.5, and x + y + z is 1; m is 1.05 to 1.25; n is 0.05 to 0.5.
10. Use of the fluorinated high nickel ternary material according to claim 9 in the field of lithium ion batteries.
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