CN105070903A - Ternary cathode material precursor, preparation method and application thereof - Google Patents
Ternary cathode material precursor, preparation method and application thereof Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention provides a ternary cathode material precursor, a preparation method and an application thereof. The method comprises the following steps: firstly, preparing a mixed metal salt solution, and adjusting the pH value to be 0.1-5.0; removing impurities through an exchange column filled with cation exchange resin; and finally pumping the obtained material, a complexing agent and a precipitant into a coprecipitation reaction kettle simultaneously, and synthesizing a high-quality ternary cathode material precursor with extremely low impurity content through a controlled crystallization method, wherein the chemical formula of the precursor is NixCoyMnz(OH)2; x is less than 1 and greater than or equal to 0.3; y is less than or equal to 0.5 and greater than or equal to 0.05; and x+y+z is equal to 1. Through removing impurities from the mixed metal salt solution, the impurity content in the ternary cathode material precursor is greatly reduced; and the safety performance and the electrochemical property of the ternary cathode material are improved.
Description
Technical field
The invention belongs to field of lithium ion secondary, relate to a kind of ternary anode material precursor, preparation method and its usage, be specifically related to a kind of high-quality ternary anode material precursor, preparation method and its usage.
Background technology
Current business-like anode material for lithium-ion batteries mainly contains cobalt acid lithium, spinel lithium manganate, ternary material and LiFePO4 etc.Preparation technology is simple for cobalt acid lithium, and charging/discharging voltage is higher, and cycle performance is excellent and obtain extensive use, but the price is rather stiff of cobalt and constantly going up, and the reserves of China are little, this makes the development cost of lithium cobaltate cathode material high, be approximately the 5-6 of lead-acid battery doubly, 2 times of Ni-MH battery.The LiMn2O4 of spinel structure has cheap, resourceful advantage, but the capacity attenuation of spinelle manganic acid lithium material is very fast, especially in cycle performance sharp fall and the poor storage performance of high temperature (more than 60 DEG C).LiFePO4 thermal stability, fail safe and cycle life are good, but it is very low also to there is electronic conductance, are unfavorable for the defects such as slow, the desirable LiFePO4 of reversible reaction and lithium ion diffusion wherein not easily synthesizes.Lithium nickel cobalt manganese oxide (is called for short ternary material, LiNi
xco
ymn
zo
2) have both the advantage of cobalt acid lithium, lithium nickelate and LiMn2O4 three preferably, compensate for respective deficiency.
The quality of tertiary cathode material performance depends primarily on the quality of ternary anode material precursor.At present, the ternary anode material precursor impurity content that domestic manufacturer produces is generally higher, especially the impurity such as Fe, Cr, Cu and Zn of battery safety are affected, these foreign metals can stripping in battery charge and discharge process, moves to negative pole and separate out to form dendrite, and these foreign metal dendrite can pierce through barrier film and cause battery micro-short circuit, battery core temperature is caused to raise, worsen battery performance, even cause battery thermal runaway, finally cause cells burst to explode.Therefore, reduce impurity content in ternary anode material precursor, most important to the tertiary cathode material obtaining high security and excellent electrochemical performance.
In order to solve the problem, CN103545503A proposes in precipitation reagent, add bismuth oxide, magnesium hydroxide or ammonium fluoride.Although this method can go out the iron in reaction system, also increase the risk introducing bismuth and magnesium addition.In addition, ammonium fluoride is used to introduce a large amount of fluorine ions, for later stage sewage disposal adds work difficulty.And above method also can only remove single iron tramp.Therefore, the method more effectively removing metal impurities in ternary anode material precursor is necessary to develop.
Summary of the invention
For the problem that metals content impurity in existing ternary anode material precursor is higher, an object of the present invention is the preparation method providing a kind of high-quality ternary anode material precursor, ternary anode material precursor metals content impurity prepared by the method is extremely low, the impurity contents such as Fe, Cr, Cu and Zn, all at below 5ppm, improve security performance and the chemical property of tertiary cathode material.Further, the method technique is simple, is easy to realization of industrialization.
To achieve these goals, present invention employs following technical scheme:
A preparation method for ternary anode material precursor, comprises the following steps:
(1) mixed salt solution of nickel salt, cobalt salt and manganese salt is carried out removal of impurities by the exchange column that cation exchange resin is housed, to remove the foreign ions such as Fe, Cr, Cu and Zn, and obtain solution A;
(2) under protective atmosphere, solution A, complexing agent and precipitation reagent are pumped into coprecipitation reaction still simultaneously and carries out coprecipitation reaction, and then obtain ternary anode material precursor.
In the present invention, described " removal of impurities " namely carried out the removal of the foreign ions such as Fe, Cr, Cu and Zn except Ni, Co and Mn by the exchange column that cation exchange resin is housed.
Preferably, nickel salt described in step (1) is the mixing of a kind of in nickelous sulfate, nickel chloride, nickel nitrate or nickel acetate or at least two kinds.
Preferably, cobalt salt described in step (1) is the combination of a kind of in cobaltous sulfate, cobalt chloride, cobalt nitrate or cobalt acetate or at least two kinds.
Preferably, manganese salt described in step (1) is the combination of a kind of in manganese sulfate, manganese chloride, manganese nitrate or manganese acetate or at least two kinds.
The present invention is by carrying out removal of impurities by the mixed salt solution of nickel salt, cobalt salt and manganese salt by the exchange column that cation exchange resin is housed, better to remove the impurity such as Fe, Cr, Cu and Zn in solution, reduce the impurity content such as Fe, Cr, Cu and Zn in ternary anode material precursor.Meanwhile, cation exchange resin also can regenerate to be recycled, and use cost is very low, is easy to suitability for industrialized production.
In the present invention, cation exchange resin described in step (1) is formed primarily of three-dimensional network polymer skeleton and the functional group be entrenched on polymer backbone, three-dimensional network polymer skeleton is any one in polystyrene, polyacrylic acid, polyacrylate or phenolic aldehyde, and functional group is any one in sulfonic group, carboxyl or iminodiacetic acid (salt) acidic group.
Exemplary cation exchange resin is: three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl; Three-dimensional network polymer skeleton: phenolic aldehyde, functional group: iminodiacetic acid (salt) acidic group; Three-dimensional network polymer skeleton: polystyrene, functional group: carboxyl; Three-dimensional network polymer skeleton: polyacrylic acid, functional group: sulfonic group.
Dissimilar cation exchange resin is different to the disposal ability of different metal impurity, such as: functional group is sulfonic gel-network precipitation method (three-dimensional network polymer skeleton be in polystyrene, polyacrylic acid, polyacrylate or phenolic aldehyde any one) to removal chromium (Cr) and copper (Cu) ion energy especially by force, and relatively weak to other metal (Fe and Zn etc.) selectivity; And polystyrene-based cation exchange resin (functional group be in sulfonic group, carboxyl or iminodiacetic acid (salt) acidic group any one) deironing (Fe) ability with strong oxidizing property is strong especially.Therefore, according to the number of the content of impurity each in mixed salt solution, suitable cation exchange resin can be selected.Such as, Cr and the Cu impurity content in mixed salt solution is higher, and other content are less, then the functional group stronger to Cr and Cu ion remaval ability can be selected to be sulfonic gel-network precipitation method.
Under the cation exchange resin condition using same kind, the pH value height of processed mixed salt solution also can affect the effect of removing Fe, Cr, Cu and Zn foreign ion.Therefore, in order to improve the removal effect of cation exchange resin to Fe, Cr, Cu and Zn foreign ion, need to adjust mixed salt solution to suitable pH value, the pH value of preferred adjustment mixed salt solution is 0.1 ~ 5, such as 0.4,0.8,1.2,1.6,1.8,2.2,2.6,3,3.4,3.8,4,4.4 or 4.8, preferably 0.5 ~ 4.
Preferably, cation exchange resin is formed primarily of three-dimensional network polymer skeleton and the functional group be entrenched on polymer backbone, three-dimensional network polymer skeleton is any one in polystyrene, polyacrylic acid, polyacrylate or phenolic aldehyde, functional group is iminodiacetic acid (salt) acidic group, when the pH of mixed salt solution is 2 ~ 4, except Fe effect is better, when pH is 3 ~ 4, except Cu is effective.And as pH > 4, the part Mn ion in solution will be removed.
Preferably, the pH value of mixed salt solution is regulated in step (1) by acid adding.Preferably, described acid is any one in nitric acid, sulfuric acid or hydrochloric acid.
Preferably, mixed salt solution is carried out removal of impurities with the flow velocity of 0.1 ~ 0.5L/min by the exchange column that cation exchange resin is housed by step (1).The present invention adopts low flow velocity (0.1 ~ 0.5L/min) by the mode of cation exchange resin column, significantly improves the effect of removal of impurities.
Preferably, step (1) described exchange column is 4 ~ 6 grades of series connection, and exchange column is equipped with at least two kinds (two or more) different types of cation exchange resin.Exemplary as described in exchange column two kinds of different types of cation exchange resins be housed refer to: be 4 grades of series connection for exchange column, namely wherein 1,2 or 3 grade adopts the cation exchange resin of a type, in addition 3, the 2 or 1 grades cation exchange resins adopting another kind of types.
Because different types of cation exchange resin is different to the removal ability of metal, select the cooperation of different types of cation exchange resin, the degree of depth that simultaneously can realize Fe, Cr, Cu and Zn is removed.
Such as, progression can be adopted to be the exchange column of 4 grades, and two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl); Progression can also be adopted to be the exchange column of 6 grades, and two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: phenolic aldehyde, functional group: iminodiacetic acid (salt) acidic group); Progression can also be adopted to be the exchange column of 5 grades, and two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: carboxyl; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: sulfonic group).
In addition, the present invention adopts low flow velocity by the mode that the exchange column of at least two kinds of different types of cation exchange resins is housed of plural serial stage, significantly improves the effect of removal of impurities.
Preferably, in step (1), mixed salt solution concentration is 0.1mol/L ~ 3mol/L.Adopt method of the present invention both can realize the removal of metal impurities in the mixed salt solution of low concentration, also can realize the high removal to metal impurities in the mixed salt solution of 3mol/L, scope applicatory is very wide.
Preferably, described in step (2), protective atmosphere is nitrogen atmosphere or argon gas atmosphere, and the flow of nitrogen and argon gas is 0.5 ~ 2L/min all independently.
Preferably, described in step (2), complexing agent is ammoniacal liquor.
Preferably, precipitation reagent described in step (2) is that NaOH is or/and potassium hydroxide.
Preferably, in the coprecipitation reaction process of step (2), controlling reaction system pH is 10 ~ 13, and to make precipitation by metallic ion complete, described pH value is such as 10.5,11,11.5,12,12.5 or 13.
Preferably, in the coprecipitation reaction process of step (2), controlling ammonia content in reaction system is 0.5g/L ~ 30g/L, such as 1g/L, 5g/L, 10g/L, 15g/L, 20g/L, 25g/L or 30g/L.
Preferably, in the coprecipitation reaction process of step (2), controlling temperature of reaction system is 45 ~ 70 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C or 70 DEG C.
Preferably, the coprecipitation reaction of step (2) carries out under agitation, and control mixing speed is 100 ~ 1000r/min.
Preferably, described method also comprises: after coprecipitation reaction terminates, and the slurry obtained is carried out to the process of ageing, washing and oven dry.
Preferably, described digestion time is 1h ~ 16h, such as 2h, 4h, 6h, 8h, 10h, 12h or 14h.
Preferably, wash to stopping during filtrate pH < 9 washing.
Preferably, bake out temperature is 100 ~ 150 DEG C, such as 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C or 145 DEG C.
Preferably, drying time is 4 ~ 12h, such as 5h, 6h, 7h, 8h, 9h, 10h or 11h.
Preferably, described ternary anode material precursor has following chemical composition: Ni
xco
ymn
z(OH)
2, 0.3≤x < 1,0.05≤y≤0.5, x+y+z=1.
Described x is such as 0.3,0.4,0.5,0.6,0.7,0.8 or 0.9.
Described y is such as 0.1,0.15,0.2,0.25,0.3,0.35,0.4 or 0.45.
As the preferred technical solution of the present invention, a kind of preparation method of matter ternary anode material precursor, comprises the following steps:
Nickel salt, cobalt salt and manganese salt are dissolved in deionized water in proportion, be mixed with uniform mixed salt solution, regulate pH value to 0.1 ~ 5.0 of mixed salt solution, carry out removal of impurities with the flow velocity of 0.1 ~ 0.5L/min by the exchange column that cation exchange resin is housed, obtain solution A;
Under protective atmosphere, solution A, complexing agent and precipitation reagent are pumped in coprecipitation reaction still simultaneously and carry out coprecipitation reaction, in course of reaction, pH value of reaction system controls 10.0 ~ 13.0, ammonia content controls at 0.5g/L ~ 30g/L, temperature controls at 45 DEG C ~ 70 DEG C, and mixing speed controls at 100 ~ 1000r/min;
After coprecipitation reaction terminates, carry out ageing, washing and oven dry, obtain ternary anode material precursor to the slurry obtained, its chemical formula is Ni
xco
ymn
z(OH)
2, 0.3≤x < 1,0.05≤y≤0.5, x+y+z=1.
In above-mentioned optimal technical scheme, first hybrid metal mixed salt solution is prepared, adjust ph to 0.1 ~ 5.0, then the exchange column by being equipped with cation exchange resin carries out removal of impurities, last pump into coprecipitation reaction still with complexing agent and precipitation reagent simultaneously, by crystallization control method, synthesize the high-quality ternary anode material precursor that impurity content is extremely low, the impurity contents such as Fe, Cr, Cu and Zn, all at below 5ppm, improve security performance and the chemical property of tertiary cathode material.
Two of object of the present invention is to provide a kind of ternary anode material precursor adopting method described above to prepare, and it has following chemical composition: Ni
xco
ymn
z(OH)
2, 0.3≤x < 1,0.05≤y≤0.5, the impurity content such as x+y+z=1, Fe, Cr, Cu and Zn is all at below 5ppm.
Three of object of the present invention is to provide the purposes of a kind of ternary anode material precursor as above in lithium ion battery.
Compared with the prior art, the present invention has following beneficial effect:
In ternary anode material precursor prepared by the present invention, Fe, Cr, Cu, Zn impurity content is extremely low, all at below 5ppm, considerably reduces the security risk in use procedure, and it improves more greatly its chemical property simultaneously.And the method technique is simple, and cation exchange resin also can regenerate to be recycled, and use cost is very low, is easy to suitability for industrialized production.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1
By nickelous sulfate, cobaltous sulfate and manganese sulfate in molar ratio 1:1:1 weigh, then be dissolved in deionized water to be mixed with and to mix the mixed salt solution that concentration is 1.5mol/L, by dilute sulfuric acid adjust ph to 1.0, take flow velocity as 0.2L/min be the exchange column of 4 grades by progression, two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl), the mixed solution after removal of impurities is denoted as solution A.Solution A, ammoniacal liquor are pumped in coprecipitation reaction still together with NaOH and carry out coprecipitation reaction; in course of reaction, pH value of reaction system controls 10.8; in reaction system, ammonia content controls at 2g/L; temperature of reaction system controls at 55 DEG C; mixing speed 400r/min; pass into argon shield, argon flow amount 0.6mL/min.After coprecipitation reaction terminates, mechanical agitation is continued to the slurry obtained, ageing 100min under 55 DEG C of conditions, then spend deionized water, wash to filtrate pH=8.2, dry 4h for 120 DEG C, 200 mesh sieves divide, and obtain the ternary anode material precursor that impurity content is extremely low.
Embodiment 2
By nickel chloride, cobalt chloride and manganese chloride in molar ratio 5:2:3 weigh, then be dissolved in deionized water to be mixed with and to mix the mixed salt solution that concentration is 1.0mol/L, by watery hydrochloric acid adjust ph to 3.0, take flow velocity as 0.4L/min be the exchange column of 6 grades by progression, two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: phenolic aldehyde, functional group: iminodiacetic acid (salt) acidic group), the mixed solution after removal of impurities is denoted as solution A.Solution A, ammoniacal liquor are pumped in coprecipitation reaction still together with NaOH and carry out coprecipitation reaction; in course of reaction, pH value of reaction system controls 11.2; in reaction system, ammonia content controls at 5g/L; temperature of reaction system controls at 50 DEG C; mixing speed 600r/min; pass into argon shield, argon flow amount 1.6mL/min.After coprecipitation reaction terminates, continue mechanical agitation to the slurry obtained, ageing 2h under 50 DEG C of conditions, then spends deionized water, washs to filtrate pH=8.6, and dry 8h for 130 DEG C, 200 mesh sieves divide, and obtain the ternary anode material precursor that impurity content is extremely low.
Embodiment 3
By nickel nitrate, cobalt nitrate and manganese nitrate in molar ratio 6:2:2 weigh, then be dissolved in deionized water to be mixed with and to mix the mixed salt solution that concentration is 2.0mol/L, by dust technology adjust ph to 4.0, take flow velocity as 0.3L/min be the exchange column of 5 grades by progression, two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: carboxyl; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: sulfonic group), the mixed solution after removal of impurities is denoted as solution A.By solution A, ammoniacal liquor is pumped in coprecipitation reaction still and carries out coprecipitation reaction together with NaOH, in course of reaction, pH value of reaction system controls 11.6, in reaction system, ammonia content controls at 7g/L, temperature of reaction system controls at 60 DEG C, mixing speed 500r/min, pass into argon shield, argon flow amount 1.2mL/min, after coprecipitation reaction terminates, mechanical agitation is continued to the slurry obtained, ageing 3h under 60 DEG C of conditions, then deionized water is spent, washing is to filtrate pH=8.0, dry 4h for 120 DEG C, 200 mesh sieves divide, obtain the ternary anode material precursor that impurity content is extremely low.
Embodiment 4
All the other are identical with embodiment 1, regulate pH to 4.5 except with dilute sulfuric acid.
Can be found by the comparison of embodiment 1 with embodiment 4, pH value affects final impurity-eliminating effect, and impurity-eliminating effect pH value being adjusted to 1.0 is significantly better than 4.5.
Embodiment 5
All the other are identical with embodiment 1, and except exchange column replaces with single-stage exchange column, and two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl).
Embodiment 6
All the other are identical with embodiment 1, and except filling a kind of cation exchange resin in exchange column, cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group.
Embodiment 7
All the other are identical with embodiment 1, and except filling a kind of cation exchange resin in exchange column, cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl.
Can be found by the contrast of embodiment 1 with embodiment 5 ~ 7, adopt plural serial stage form, and two kinds of different types of cation exchange resins are housed, the removal effect of impurity metal ion can be improved further.
Embodiment 8
All the other are identical with embodiment 1, are except the exchange column of 4 grades except being 1L/min with flow velocity by mixed salt solution by progression.
Contrast can find by embodiment 1 technique effect with embodiment 8, by mixed salt solution with lower flow velocity and plural serial stage passes through exchange column, the impurity-eliminating effect of metal ion can be improved further.
Embodiment 9
All the other are identical with embodiment 1, fill three kinds of cation exchange resins, be respectively: a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group except in exchange column; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: iminodiacetic acid (salt) acidic group; The third cation exchange resin is three-dimensional network polymer skeleton: phenolic aldehyde, functional group: carboxyl.
Embodiment 10
By nickelous sulfate, cobaltous sulfate and manganese sulfate in molar ratio 3:5:2 weigh, then be dissolved in deionized water to be mixed with and to mix the mixed salt solution that concentration is 3mol/L, by dilute sulfuric acid adjust ph to 0.1, take flow velocity as 0.1L/min be the exchange column of 4 grades by progression, two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl), the mixed solution after removal of impurities is denoted as solution A.Solution A, ammoniacal liquor are pumped in coprecipitation reaction still together with NaOH and carry out coprecipitation reaction; in course of reaction, pH value of reaction system controls 13; in reaction system, ammonia content controls at 0.5g/L; temperature of reaction system controls at 45 DEG C; mixing speed 100r/min; pass into argon shield, argon flow amount 0.5mL/min.After coprecipitation reaction terminates, continue mechanical agitation to the slurry obtained, ageing 1h under 55 DEG C of conditions, then spends deionized water, washs to filtrate pH=8.2, and dry 12h for 100 DEG C, 200 mesh sieves divide, and obtain the ternary anode material precursor that impurity content is extremely low.
Embodiment 11
By nickelous sulfate, cobaltous sulfate and manganese sulfate in molar ratio 8:1:1 weigh, then be dissolved in deionized water to be mixed with and to mix the mixed salt solution that concentration is 0.1mol/L, by dilute sulfuric acid adjust ph to 5, take flow velocity as 0.5L/min be the exchange column of 4 grades by progression, two kinds of cation exchange resins are housed in exchange column, and (a kind of cation exchange resin is three-dimensional network polymer skeleton: polystyrene, functional group: sulfonic group; Another kind of cation exchange resin is three-dimensional network polymer skeleton: polyacrylic acid, functional group: carboxyl), the mixed solution after removal of impurities is denoted as solution A.Solution A, ammoniacal liquor are pumped in coprecipitation reaction still together with NaOH and carry out coprecipitation reaction; in course of reaction, pH value of reaction system controls 12; in reaction system, ammonia content controls at 30g/L; temperature of reaction system controls at 70 DEG C; mixing speed 1000r/min; pass into argon shield, argon flow amount 2mL/min.After coprecipitation reaction terminates, continue mechanical agitation to the slurry obtained, ageing 16h under 55 DEG C of conditions, then spends deionized water, washs to filtrate pH=8.2, and dry 4h for 150 DEG C, 200 mesh sieves divide, and obtain the ternary anode material precursor that impurity content is extremely low.
Comparative example 1
By nickelous sulfate, cobaltous sulfate, manganese sulfate in molar ratio 1:1:1 weigh, be then dissolved in deionized water and be mixed with and mix the salting liquid that concentration is 1.5mol/L, this mixed solution is denoted as solution A; Solution A, ammoniacal liquor are pumped in coprecipitation reaction still together with NaOH and carry out coprecipitation reaction; in course of reaction, reacting system PH value controls 10.8; in reaction system, ammonia content controls at 2g/L; temperature of reaction system controls at 55 DEG C; mixing speed 400r/min; pass into argon shield; flow 0.6mL/min, after coprecipitation reaction terminates, continues mechanical agitation to the slurry obtained; ageing 100min under 55 DEG C of conditions; then spend deionized water, wash filtrate pH=8.2, dry 4h for 120 DEG C; 200 mesh sieves divide, and both obtain ternary anode material precursor.
By the technique effect comparison of embodiment 1 with comparative example 1, can learn, comparative example 1 not by mixed salt solution by being equipped with the exchange column of cation exchange resin, and directly carry out coprecipitation reaction, in the ternary anode material precursor obtained, impurity content is apparently higher than embodiment 1.
The different embodiment of table 1 and comparative example gained ternary anode material precursor impurity content list
| Example | Chemical formula | Fe(％) | Cr(％) | Cu(％) | Zn(％) |
| Embodiment 1 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0004 | 0.0002 | 0.0001 | 0.0003 |
| Embodiment 2 | Ni 0.5Co 0.2Mn 0.3(OH) 2 | 0.0002 | 0.0001 | 0.0001 | 0.0002 |
| Embodiment 3 | Ni 0.6Co 0.2Mn 0.2(OH) 2 | 0.0004 | 0.0002 | 0.0003 | 0.0004 |
| Embodiment 4 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0007 | 0.0005 | 0.0008 | 0.0006 |
| Embodiment 5 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0005 | 0.0003 | 0.0005 | 0.0004 |
| Embodiment 6 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0004 | 0.0004 | 0.0006 | 0.0005 |
| Embodiment 7 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0006 | 0.0004 | 0.0004 | 0.0004 |
| Embodiment 8 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0007 | 0.0003 | 0.0002 | 0.0004 |
| Embodiment 9 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0005 | 0.0002 | 0.0001 | 0.0003 |
| Embodiment 10 | Ni 0.3Co 0.5Mn 0.2(OH) 2 | 0.0005 | 0.0003 | 0.0002 | 0.0003 |
| Embodiment 11 | Ni 0.8Co 0.1Mn 0.1(OH) 2 | 0.0008 | 0.0006 | 0.0007 | 0.0007 |
| Comparative example 1 | Ni 1/3Co 1/3Mn 1/3(OH) 2 | 0.0039 | 0.0026 | 0.0030 | 0.0036 |
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for ternary anode material precursor, is characterized in that, comprises the following steps:
(1) mixed salt solution of nickel salt, cobalt salt and manganese salt is carried out removal of impurities by the exchange column that cation exchange resin is housed, obtain solution A;
(2) under protective atmosphere, solution A, complexing agent and precipitation reagent are pumped into coprecipitation reaction still simultaneously and carries out coprecipitation reaction, and then obtain ternary anode material precursor.
2. the method for claim 1, is characterized in that, nickel salt described in step (1) is the mixing of a kind of in nickelous sulfate, nickel chloride, nickel nitrate or nickel acetate or at least two kinds;
Preferably, cobalt salt described in step (1) is the combination of a kind of in cobaltous sulfate, cobalt chloride, cobalt nitrate or cobalt acetate or at least two kinds;
Preferably, manganese salt described in step (1) is the combination of a kind of in manganese sulfate, manganese chloride, manganese nitrate or manganese acetate or at least two kinds.
3. method as claimed in claim 1 or 2, it is characterized in that, cation exchange resin described in step (1) is formed primarily of three-dimensional network polymer skeleton and the functional group be entrenched on polymer backbone, three-dimensional network polymer skeleton is any one in polystyrene, polyacrylic acid, polyacrylate or phenolic aldehyde, and functional group is any one in sulfonic group, carboxyl or iminodiacetic acid (salt) acidic group;
Preferably, step (1) regulates the pH value of mixed salt solution to be 0.1 ~ 5, and preferably 0.5 ~ 4;
Preferably, cation exchange resin is formed primarily of three-dimensional network polymer skeleton and the functional group be entrenched on polymer backbone, three-dimensional network polymer skeleton is any one in polystyrene, polyacrylic acid, polyacrylate or phenolic aldehyde, functional group is iminodiacetic acid (salt) acidic group, and step (1) regulates the pH value of mixed salt solution to be 2 ~ 4;
Preferably, cation exchange resin is formed primarily of three-dimensional network polymer skeleton and the functional group be entrenched on polymer backbone, three-dimensional network polymer skeleton is any one in polystyrene, polyacrylic acid, polyacrylate or phenolic aldehyde, functional group is iminodiacetic acid (salt) acidic group, and step (1) regulates the pH value of mixed salt solution to be 3 ~ 4;
Preferably, the pH value of mixed salt solution is regulated in step (1) by acid adding;
Preferably, described acid is any one in nitric acid, sulfuric acid or hydrochloric acid.
4. the method as described in one of claim 1-3, is characterized in that, mixed salt solution is carried out removal of impurities with the flow velocity of 0.1 ~ 0.5L/min by the exchange column that cation exchange resin is housed by step (1);
Preferably, step (1) described exchange column is 4 ~ 6 grades of series connection, and exchange column is equipped with at least two kinds of different types of cation exchange resins;
Preferably, in step (1), mixed salt solution concentration is 0.1mol/L ~ 3mol/L.
5. the method as described in one of claim 1-4, is characterized in that, described in step (2), protective atmosphere is nitrogen atmosphere or argon gas atmosphere, and the flow of nitrogen and argon gas is 0.5 ~ 2L/min all independently;
Preferably, described in step (2), complexing agent is ammoniacal liquor;
Preferably, precipitation reagent described in step (2) is that NaOH is or/and potassium hydroxide;
Preferably, in the coprecipitation reaction process of step (2), controlling reaction system pH is 10 ~ 13;
Preferably, in the coprecipitation reaction process of step (2), controlling ammonia content in reaction system is 0.5g/L ~ 30g/L;
Preferably, in the coprecipitation reaction process of step (2), controlling temperature of reaction system is 45 ~ 70 DEG C;
Preferably, the coprecipitation reaction of step (2) carries out under agitation, and control mixing speed is 100 ~ 1000r/min.
6. the method as described in one of claim 1-5, is characterized in that, described method also comprises: after coprecipitation reaction terminates, and the slurry obtained is carried out to the process of ageing, washing and oven dry;
Preferably, described digestion time is 1h ~ 16h;
Preferably, wash to stopping during filtrate pH < 9 washing;
Preferably, bake out temperature is 100 ~ 150 DEG C;
Preferably, drying time is 4 ~ 12h.
7. the method as described in one of claim 1-6, is characterized in that, described ternary anode material precursor has following chemical composition: Ni
xco
ymn
z(OH)
2, 0.3≤x < 1,0.05≤y≤0.5, x+y+z=1.
8. the method as described in one of claim 1-7, is characterized in that, said method comprising the steps of:
A nickel salt, cobalt salt and manganese salt are dissolved in deionized water by () in proportion, be mixed with uniform mixed salt solution, regulate pH value to 0.1 ~ 5.0 of mixed salt solution, carry out removal of impurities with the flow velocity of 0.1 ~ 0.5L/min by the exchange column that cation exchange resin is housed, obtain solution A;
B () is under protective atmosphere, solution A, complexing agent and precipitation reagent are pumped in coprecipitation reaction still simultaneously and carry out coprecipitation reaction, in course of reaction, pH value of reaction system controls 10.0 ~ 13.0, ammonia content controls at 0.5g/L ~ 30g/L, temperature controls at 45 DEG C ~ 70 DEG C, and mixing speed controls at 100 ~ 1000r/min;
C (), after coprecipitation reaction terminates, is carried out ageing, washing and oven dry to the slurry obtained, is obtained ternary anode material precursor, its chemical formula is Ni
xco
ymn
z(OH)
2, 0.3≤x < 1,0.05≤y≤0.5, x+y+z=1.
9. adopt the ternary anode material precursor that method prepares as described in one of claim 1-8, it has following chemical composition: Ni
xco
ymn
z(OH)
2, 0.3≤x < 1,0.05≤y≤0.5, x+y+z=1, Fe, Cr, Cu and Zn impurity content are all at below 5ppm.
10. the purposes of a ternary anode material precursor as claimed in claim 9 in lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106830106A (en) * | 2017-03-23 | 2017-06-13 | 中南大学 | A kind of method for removing lithium ion battery ternary material precursor impurity |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182379A (en) * | 1995-04-24 | 1998-05-20 | 亨凯尔公司 | Process for separating multivalent metal ions from autodeposition compositions |
| CN101020650A (en) * | 2007-03-21 | 2007-08-22 | 中国科学院上海有机化学研究所 | Process of eliminating iron ion from acrylonitrile product |
| CN101367860A (en) * | 2008-09-27 | 2009-02-18 | 南京工业大学 | Method for separating and extracting beta-sitosterol from mixed phytosterin |
| CN101497051A (en) * | 2009-01-20 | 2009-08-05 | 南京大学 | Composite cationic ion-exchange resin supporting iron-series duplex metal nano granules as well as preparation method and use thereof |
| CN102676814A (en) * | 2012-06-06 | 2012-09-19 | 金柯有色金属有限公司 | Method for removing impurity ferrum in nickel sulfate solution |
| CN103545503A (en) * | 2012-07-17 | 2014-01-29 | 河南科隆集团有限公司 | Preparation method of low iron content ternary precursor |
| JP2014088284A (en) * | 2012-10-30 | 2014-05-15 | Rin Kagaku Kogyo Kk | Method for refining phosphoric acid solution, phosphate, and method for producing the same |
| JP2015056275A (en) * | 2013-09-11 | 2015-03-23 | 旭硝子株式会社 | Process of manufacturing positive electrode active material for lithium ion secondary battery and process of manufacturing positive electrode for lithium ion secondary battery |
-
2015
- 2015-07-21 CN CN201510429951.5A patent/CN105070903B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182379A (en) * | 1995-04-24 | 1998-05-20 | 亨凯尔公司 | Process for separating multivalent metal ions from autodeposition compositions |
| CN101020650A (en) * | 2007-03-21 | 2007-08-22 | 中国科学院上海有机化学研究所 | Process of eliminating iron ion from acrylonitrile product |
| CN101367860A (en) * | 2008-09-27 | 2009-02-18 | 南京工业大学 | Method for separating and extracting beta-sitosterol from mixed phytosterin |
| CN101497051A (en) * | 2009-01-20 | 2009-08-05 | 南京大学 | Composite cationic ion-exchange resin supporting iron-series duplex metal nano granules as well as preparation method and use thereof |
| CN102676814A (en) * | 2012-06-06 | 2012-09-19 | 金柯有色金属有限公司 | Method for removing impurity ferrum in nickel sulfate solution |
| CN103545503A (en) * | 2012-07-17 | 2014-01-29 | 河南科隆集团有限公司 | Preparation method of low iron content ternary precursor |
| JP2014088284A (en) * | 2012-10-30 | 2014-05-15 | Rin Kagaku Kogyo Kk | Method for refining phosphoric acid solution, phosphate, and method for producing the same |
| JP2015056275A (en) * | 2013-09-11 | 2015-03-23 | 旭硝子株式会社 | Process of manufacturing positive electrode active material for lithium ion secondary battery and process of manufacturing positive electrode for lithium ion secondary battery |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830106A (en) * | 2017-03-23 | 2017-06-13 | 中南大学 | A kind of method for removing lithium ion battery ternary material precursor impurity |
| CN106830106B (en) * | 2017-03-23 | 2018-03-30 | 中南大学 | A kind of method for removing lithium ion battery ternary material precursor impurity |
| CN107399766A (en) * | 2017-06-19 | 2017-11-28 | 金驰能源材料有限公司 | A kind of preparation method of spherical nickel cobalt manganese persursor material |
| CN107507970A (en) * | 2017-08-25 | 2017-12-22 | 北方奥钛纳米技术有限公司 | The preparation method of nickel cobalt manganese hydroxide precursor and nickel cobalt manganese hydroxide precursor and application |
| CN107611423A (en) * | 2017-08-28 | 2018-01-19 | 浙江新时代海创锂电科技有限公司 | A kind of preparation method of nickel-cobalt-manganese ternary presoma |
| CN108365214A (en) * | 2017-12-28 | 2018-08-03 | 宁夏东方钽业股份有限公司 | A kind of high-performance small particle ternary anode material precursor and preparation method thereof |
| CN108963218A (en) * | 2018-07-09 | 2018-12-07 | 王丹亮 | A kind of preparation method and application of the nickelic ternary lithium of low cobalt |
| CN112234187A (en) * | 2020-10-19 | 2021-01-15 | 南通金通储能动力新材料有限公司 | Sulfur and sodium removing method for ternary precursor |
| CN115594233A (en) * | 2022-11-07 | 2023-01-13 | 湖州超钠新能源科技有限公司（Cn） | Quaternary positive electrode material precursor of sodium-ion battery, and preparation method and application thereof |
| CN115747521A (en) * | 2022-12-29 | 2023-03-07 | 江苏电科环保有限公司 | Method for recovering and preparing lithium carbonate from waste lithium ion battery positive electrode material |
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