CN109768272A - A kind of richness lithium tertiary cathode material and its environment-friendly preparation method thereof - Google Patents
A kind of richness lithium tertiary cathode material and its environment-friendly preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of rich lithium tertiary cathode material and its environment-friendly preparation method thereofs.This method are as follows: by configured nickel cobalt manganate solution and lithium salt solution, it is added to dissolved in the solution of surfactant and precipitating reagent, obtained mixed solution is subjected to solvent thermal reaction after being sufficiently stirred, later using obtained precursor powder is spray-dried, rich lithium tertiary cathode material xLi is obtained using roasting2MnO3(1-x) LiMO2.The resulting granular precursor of the present invention is fine and smooth, rich lithium tertiary cathode material particle diameter distribution is uniform, pattern is controllable, better crystallinity degree, and during the preparation process without a large amount of discharge of wastewater, used raw material makes in calcination process without noxious gas emission, it is environmentally protective, preparation process is simple, is easy to industrialize；Using for novel surfactant effectively makes slurry be uniformly dispersed, and there is stable mixed phase in obtained positive electrode grain edges, the side reaction of positive electrode and electrolyte is reduced, resulting positive electrode has the important advantages such as specific discharge capacity height, good cycling stability.
Description
Technical field
The invention belongs to new energy materials fields, and in particular to a kind of rich lithium tertiary cathode material of high performance lithium ion battery
The preparation method of material and its green production.
Background technique
With electric car, the fast development of smart grid and extensive energy storage field, existing existing battery system is got over
It lives the needs of production to be more difficult to meet people, and rich lithium tertiary cathode material (xLi2MnO3·(1-x)LiMO2, M=Ni,
Co, Mn, etc.) because its higher specific capacity, high operating voltage and advantages of environment protection be considered as high-capacity lithium ion battery from
One of the positive electrode system with application prospect is most studied in sub- secondary cell.The main preparation methods of richness lithium material at present
Have: high temperature solid-state method, sol-gal process, coprecipitation, solvent-thermal method etc., but these methods still have shortcomings, such as: energy
Consumption is high, has a large amount of discharge of wastewater in production process, these disadvantages considerably increase production cost and cause environmental pollution.
In order to solve these problems, people have carried out a large amount of exploration work in terms of technology of preparing, achieve some important progress.
It is rich that 104882599 A of CN of Chinese invention patent Liao Shijun seminar application proposes a kind of spray drying preparation
The method of lithium tertiary cathode material, applicant is using oxalic acid and ammonium oxalate as precipitating reagent, with Ni, the nitrate and hydrogen of Co, Mn
The slurry of oxalates has been made as raw material in lithia, has then obtained rich lithium tertiary cathode material by spray drying, roasting
Material, this technique simplifies the preparation processes of rich lithium ternary material, solve the problems, such as a large amount of waste discharges of traditional handicraft, preparation
Positive electrode performance is also very excellent.There are problems to be merely using deionized water as solvent for the technology of this application, the anode of preparation
There are particle agglomerations that serious, pattern is difficult to for material, leads to problems such as cycle performance, high rate performance poor, and the present invention with
The mixed solution of deionized water and organic solvent is solvent, and the method for combining spray drying effectively improves synthesis material
The agglomeration problem of material, the material morphology of synthesis is controllable, and particle diameter distribution is uniform, to improve the chemical property of material；
And this application technology needs to adjust pH value of solution, but production technology according to the invention, the final pH of slurry with citric acid or ammonium hydroxide
Between 8.5~9, while avoiding Acid Slurry from corroding equipment, production technology is also simplified.Meanwhile the present invention uses
Raw material make that the exhaust gas containing oxynitrides will not be discharged in roasting process, cause environmental pollution, it is more environmentally protective.
108063226 A of Chinese invention patent application CN proposes one step sol method of one kind and prepares high capacity richness lithium ternary
The method of positive electrode, applicant adjust solution ph using citric acid or glucose as chelating agent, with ammonium hydroxide, then stir
To sol form, rich lithium tertiary cathode material, synthetic product specific capacity with higher finally has been made by spray drying, roasting
With preferable high rate performance.Although sol-gal process have the advantages that it is as described above, in preparation process again there are the volatilizations of ammonium hydroxide
It causes environmental pollution, seriously endanger human health, and preparation process needs to control pH, makes anode complicated for operation, to prepare
Material particle size is unevenly distributed, and there is a problem of that cycle performance is poor.Therefore, it is simple, environmentally protective to seek a kind of preparation process, and
The positive electrode with excellent electrochemical performance, which is made, highly important realistic meaning.
Summary of the invention
It is an object of the invention to overcome defect of the existing technology, optimize preparation process, provides a kind of rich lithium three
The preparation method of first positive electrode and its green production.
Technical solution of the present invention is as follows.
A kind of richness lithium tertiary cathode material, the positive electrode are layer structure, general formula are as follows: xLi2MnO3·(1-x)
LiMO2, wherein 0 < x < 1, M=MnaNibCo(1-a-b), 0 < a < 1,0 <b≤0.5.
A kind of environment-friendly preparation method thereof of richness lithium tertiary cathode material, comprising the following steps:
(1) surfactant is dissolved in solvent, the solvent be deionized water, organic solvent or deionized water with have
The mixed solution of solvent adds precipitating reagent stirring and dissolving, wiring solution-forming A；
(2) lithium salts is dissolved in wiring solution-forming B in deionized water；
It (3) is a:b:(1- according to the molar ratio of the rich lithium ternary material molecular formula by manganate, nickelate, cobaltatess
A-b), wherein 0 < a < 1,0 <b≤0.5 are dissolved in wiring solution-forming C in deionized water；
(4) solution B, solution C are successively added dropwise to solution A dropwise, the organic solvent of addition, stirring 1-2h react to be formed it is mixed
Close solution D；The additive amount of the organic solvent accounts for the 5%~20% of solution A, solution B and solution C total volume；
(5) then solution D is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, carries out solvent thermal reaction
Slurry E is made；
(6) slurry E made from step (5) is spray-dried, obtains rich lithium ternary material precursor powder；
(7) richness lithium ternary material precursor dried powder made from step (6) is ground, roasts, is cooled to room temperature
Obtaining general formula afterwards is xLi2MnO3·(1-x)LiMO2Stratiform richness lithium ternary material.
In the above method, in step (1), the surfactant is cetyl trimethylammonium bromide, hydroxy ethyl fiber
Element, poloxamer, cetyl benzenesulfonic acid sodium, polyvinylpyrrolidone, lauryl sodium sulfate, polyvinyl alcohol, enuatrol, department
One or more of disk and tween；The dosage of the surfactant is the theoretical yield of rich lithium tertiary cathode material
0.1wt%-10wt%；The organic solvent be methanol, ethyl alcohol, isopropanol, polyethylene glycol, ethylene glycol, glycerine, propylene glycol,
One or more of benzyl alcohol, benzyl carbinol, dimethylformamide, acetonitrile, dimethyl sulfoxide, oleic acid and oleyl amine；The precipitating reagent
For one or more of ammonium carbonate, ammonium hydrogen carbonate, oxalic acid, urea, citric acid, ammonium formate, ammonium oxalate；The quality of the precipitating reagent
Dosage is that lithium salts and transition metal salt can be made to precipitate desired amount of 1.0-2.0 times completely.
In the above method, in step (2), the lithium salts is one of lithium acetate, lithium hydroxide, lithium nitrate, lithium carbonate
More than；The additional amount of the lithium salts is the 101wt%-110wt% of theoretical value.
In the above method, in step (3), the nickelate is nickel sulfate, nickel formate, nickel acetate, nickel chloride and nickel nitrate
One or more of；The cobaltatess are one or more of cobaltous sulfate, cobaltous formate, cobalt acetate, cobalt chloride and cobalt nitrate；It is described
Manganate is one or more of manganese sulfate, formic acid manganese, manganese acetate, manganese chloride and manganese nitrate, in mixed solution C transition metal from
Sub- total soluble matters is 0.1~2mol/L, and the transition metal ions is Ni2+、Co2+And Mn2+。
In the above method, in step (4), the dropwise addition sequence of solution is that solution B, solution C are successively added dropwise to solution dropwise
A, mixing speed 100-1000rpm/min.
In the above method, the organic solvent includes methanol, ethyl alcohol, isopropanol, polyethylene glycol, ethylene glycol, glycerine, third
One or more of glycol, benzyl alcohol, benzyl carbinol, dimethylformamide, acetonitrile, dimethyl sulfoxide, oleic acid and oleyl amine.
In the above method, the temperature of step (5) solvent thermal reaction is 90 DEG C~240 DEG C, and soaking time is 6h~48h.
In the above method, the feeding temperature of step (6) described spray drying is 170~210 DEG C, the spraying charging speed
Rate is 500-900mL/h.
In the above method, in step (7), the baking operation are as follows: by the persursor material after drying and grinding in sky
Atmosphere encloses middle 400-550 DEG C of pre-sintering 4-6h, then cools to room temperature and is ground, and is finally warming up to 800-950 DEG C of roasting 8-
16h, cooled to room temperature.
It is compared with the prior art, the present invention has the advantages that
(1) present invention uses a step solvent-thermal method, enormously simplifies preparation process, and production cost is low, and controllability is high, nothing
Discharge of wastewater discharges in roasting process without pernicious gas, is a kind of preparation process of green, may be directly applied to large-scale industry
In production, be of great practical significance.
(2) solvent thermal crystallisation is combined with spray drying, positive electrode particle diameter distribution obtained is uniform, pattern is adjustable
Control, better crystallinity degree, have been effectively relieved material agglomeration traits, have improved the stability of material structure.
(3) the material xLi prepared by the present invention2MnO3·(1-x)LiMO2The high, good cycling stability with specific discharge capacity
Etc. important advantages, be a kind of great rich lithium tertiary cathode material for having application value and prospect.
Detailed description of the invention
Fig. 1 is the XRD spectra that the embodiment of the present invention 1 prepares material；
Fig. 2 is the 0.1C discharge cycles capacity curve that the embodiment of the present invention 1 prepares material；
Fig. 3 is the 0.5C discharge cycles capacity curve that the embodiment of the present invention 1 prepares material.
Specific embodiment
It is further specific to the present invention combined with specific embodiments below to be described in detail, but embodiments of the present invention are unlimited
Routine techniques progress can refer to for not specifically specified technological parameter in this.
Embodiment 1
Prepare 0.1mol0.5Li2MnO3·0.5LiNi0.3Mn0.4Co0.3O2。
(1) by 0.7g poloxamer and 13.849g ammonium bicarbonate solubility in 100mL water, obtained solution A；
(2) 7.343g lithium hydroxide (excessive 5%) is dissolved in 40mL water, obtained solution B；
(3) 13.864g manganese acetate, 2.989g nickel acetate, 3.004g cobalt acetate are mixed and is dissolved in the water of 55mL, made
Obtain solution C；
(4) solution B is added drop-wise in solution A with 1~2 drop/s speed, formed mixed liquor, then by solution C with 1~2 drop/
The speed of s is added drop-wise in mixed liquor, and addition accounts for the ethyl alcohol of solution A, solution B and solution C total volume 5%, and stirring 2h forms stabilization
Uniform mixed solution D；
(5) mixed solution D is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, rises to 120 by room temperature
DEG C heat preservation 8h, naturally cool to room temperature and obtain slurry E；
(6) gained slurry E is spray-dried under 190 DEG C of feeding temperature and the charging rate of 800mL/h, is collected into richness
Lithium ternary anode material precursor；
(7) in air atmosphere, by 450 DEG C of roasting 5h, grinding, after 900 DEG C of roasting 12h (heating rate is 5 DEG C/
Min), rich lithium tertiary cathode material 0.5Li is obtained2MnO3·0.5LiNi0.3Mn0.4Co0.3O2。
The 0.5Li of method preparation2MnO3·0.5LiNi0.3Mn0.4Co0.3O2.Its XRD spectrum is shown in Fig. 1；Under its 0.1C multiplying power
Highest specific discharge capacity is 253.2mAh/g, as shown in Figure 2；Its 0.5C is in 90 circle of 2.0-4.8V circulation as shown in figure 3, circulation 90
Capacity retention is 87.1% after circle.The main chemical property of material is shown in Table 1.
Embodiment 2
Prepare 0.1mol 0.5Li2MnO3·0.5LiNi0.325Mn0.35Co0.325O2。
(1) by 0.7g poloxamer and 13.849g ammonium bicarbonate solubility in 100mL water, obtained solution A；
(2) 7.343g lithium hydroxide (excessive 5%) is dissolved in 40mL water, obtained solution B；
(3) 13.369g manganese acetate, 3.238g nickel acetate, 3.254g cobalt acetate are mixed and is dissolved in the water of 55mL, made
Obtain solution C；
(4) solution B is added drop-wise in solution A with 1~2 drop/s speed, formed mixed liquor, then by solution C with 1~2 drop/
The speed of s is added drop-wise in mixed liquor, and addition accounts for the ethylene glycol of solution A, solution B and solution C total volume 5%, and stirring 2h is formed surely
Fixed uniform mixed solution D；
(5) mixed solution D is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, rises to 120 by room temperature
DEG C heat preservation 8h, naturally cool to room temperature and obtain slurry E；
(6) gained slurry E is spray-dried under 190 DEG C of feeding temperature and the charging rate of 800mL/h, is collected into richness
Lithium ternary anode material precursor；
(7) in air atmosphere, by 450 DEG C of roasting 5h, grinding, after 900 DEG C of roasting 12h (heating rate is 5 DEG C/
Min), rich lithium tertiary cathode material 0.5Li is obtained2MnO3·0.5LiNi0.325Mn0.35Co0.325O2。
The main chemical property of material is shown in Table 1.
Embodiment 3
Prepare 0.1mol 0.5Li2MnO3·0.5LiN1/3Mn1/3Co1/3O2。
In addition to the cetyl trimethylammonium bromide of the quality such as use replaces poloxamer, the citric acid of 48.537g is replaced
The usage amount of manganese acetate is become 16.504g from 13.369g, the amount of nickel acetate is become from 4.151g by 13.849g ammonium hydrogen carbonate
The amount of cobalt acetate is become 4.172g from 3.254g by 2.241g, and other compositions use and preparation method is completely identical as example 2.
The main chemical property of material is shown in Table 1.
Embodiment 4
Prepare 0.1mol 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2。
In addition to replacing 13.369g manganese acetate using 18.567g manganese nitrate, 6.227g manganese nitrate replaces 3.238g nickel acetate,
16.231g lithium acetate replaces 7.343g lithium hydroxide, and hydrothermal temperature rises to 160 DEG C of heat preservation 8h by room temperature and replaces 120 DEG C of heat preservation 8h
Outside, other compositions use and preparation method is completely identical as example 2.
The main chemical property of material is shown in Table 1.
Embodiment 5
Prepare 0.1mol 0.7Li2MnO3·0.3LiNi0.3Mn0.4Co0.3O2。
In addition to the polyvinylpyrrolidone of the quality such as use replaces poloxamer, the urea of 10.617g replaces 13.849g carbon
The usage amount of manganese acetate is become 20.300g from 13.369g by sour hydrogen ammonium, and the amount of nickel acetate is become 2.241g from 3.238g, will
The amount of cobalt acetate becomes 2.253g from 2.254g, and the amount of lithium hydroxide becomes 8.356g from 7.373g, and hydrothermal temperature is by room temperature liter
Replace outside 120 DEG C of heat preservation 8h to 200 DEG C of heat preservation 8h, other compositions use and preparation method is completely identical as example 2.
The main chemical property of material is shown in Table 1.
Embodiment 6
Prepare 0.1mol 0.8Li2MnO3·0.2LiNi1/3Mn1/3Co1/3O2。
In addition to replacing 13.849g ammonium hydrogen carbonate using the oxalic acid of 22.173g, the usage amount of manganese acetate is become by 13.369g
For 21.456g, the amount of nickel acetate is become into 1.661g from 3.238g, the amount of cobalt acetate is become into 1.669g, hydrogen-oxygen from 2.254g
The amount for changing lithium becomes 8.847g from 7.373g, and hydrothermal temperature rises to 220 DEG C of heat preservation 8h by room temperature and replaces 120 DEG C of heat preservation 8h, spraying
The inlet temperature of drier is become outside 170 DEG C from 190 DEG C, and other compositions use and preparation method is completely identical as example 2.
The main chemical property of material is shown in Table 1.
Embodiment 7
Prepare 0.9Li2MnO3·0.1LiNi1/3Mn1/3Co1/3O2。
In addition to the usage amount of manganese acetate is become 23.106g from 13.369g, the amount of nickel acetate is become from 3.238g
The amount of cobalt acetate is become 0.834g from 2.254g by 0.830g, and the amount of lithium hydroxide becomes 9.339g, hydrothermal temperature from 7.373g
240 DEG C of heat preservation 8h are risen to by room temperature and replace 120 DEG C of heat preservation 8h, the inlet temperature of spray dryer becomes 180 DEG C from 190 DEG C
Outside, other compositions use and preparation method is completely identical as example 2.
The main chemical property of material is shown in Table 1.
The main chemical property table of each case study on implementation of table 1
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of richness lithium tertiary cathode material, it is characterised in that: the positive electrode is layer structure, general formula are as follows: xLi2MnO3·
(1-x) LiMO2, wherein 0 < x < 1, M=MnaNibCo(1-a-b), 0 < a < 1,0 <b≤0.5.
2. the environment-friendly preparation method thereof of richness lithium tertiary cathode material described in claim 1, which comprises the following steps:
(1) surfactant is dissolved in solvent, the solvent be deionized water, organic solvent or deionized water with it is organic molten
The mixed solution of agent adds precipitating reagent stirring and dissolving, wiring solution-forming A；
(2) lithium salts is dissolved in wiring solution-forming B in deionized water；
(3) it is a:b:(1-a-b according to the molar ratio of the rich lithium ternary material molecular formula by manganate, nickelate, cobaltatess),
Wherein 0 < a < 1,0 <b≤0.5 are dissolved in wiring solution-forming C in deionized water；
(4) solution B, solution C are successively added dropwise to solution A dropwise, the organic solvent of addition, stirring 1-2h reacts that form mixing molten
Liquid D；The additive amount of the organic solvent accounts for the 5% ~ 20% of solution A, solution B and solution C total volume；
(5) then solution D is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, carries out solvent thermal reaction and is made
Slurry E；
(6) slurry E made from step (5) is spray-dried, obtains rich lithium ternary material precursor powder；
(7) richness lithium ternary material precursor dried powder made from step (6) is ground, roasts, is cooled to after room temperature i.e.
Obtaining general formula is xLi2MnO3(1-x) LiMO2Stratiform richness lithium ternary material.
3. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that in step (1), institute
Surfactant is stated to be cetyl trimethylammonium bromide, hydroxyethyl cellulose, poloxamer, cetyl benzenesulfonic acid sodium, gather
One or more of vinylpyrrolidone, lauryl sodium sulfate, polyvinyl alcohol, enuatrol, sapn and tween；The surface is living
Property agent dosage be rich lithium tertiary cathode material theoretical yield 0.1wt%-10 wt%；The organic solvent is methanol, second
Alcohol, isopropanol, polyethylene glycol, ethylene glycol, glycerine, propylene glycol, benzyl alcohol, benzyl carbinol, dimethylformamide, acetonitrile, diformazan
One or more of base sulfoxide, oleic acid and oleyl amine；The precipitating reagent is ammonium carbonate, ammonium hydrogen carbonate, oxalic acid, urea, citric acid, first
One or more of sour ammonium, ammonium oxalate；The quality dosage of the precipitating reagent is can make lithium salts and transition metal salt precipitates institute completely
1.0-2.0 times of expense.
4. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that in step (2), institute
Stating lithium salts is one or more of lithium acetate, lithium hydroxide, lithium nitrate, lithium carbonate；The additional amount of the lithium salts is theoretical value
101wt%-110 wt%。
5. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that in step (3), institute
Stating nickelate is one or more of nickel sulfate, nickel formate, nickel acetate, nickel chloride and nickel nitrate；The cobaltatess be cobaltous sulfate,
One or more of cobaltous formate, cobalt acetate, cobalt chloride and cobalt nitrate；The manganate is manganese sulfate, formic acid manganese, manganese acetate, chlorine
Change one or more of manganese and manganese nitrate, transition metal ions total soluble matters is 0.1 ~ 2mol/L, the transition in mixed solution C
Metal ion is Ni2+、Co2+And Mn2+。
6. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that molten in step (4)
The dropwise addition sequence of liquid is that solution B, solution C are successively added dropwise to solution A, mixing speed 100-1000rpm/min dropwise.
7. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that the organic solvent
Including methanol, ethyl alcohol, isopropanol, polyethylene glycol, ethylene glycol, glycerine, propylene glycol, benzyl alcohol, benzyl carbinol, dimethyl formyl
One or more of amine, acetonitrile, dimethyl sulfoxide, oleic acid and oleyl amine.
8. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that step (5) solvent
The temperature of thermal response is 90 DEG C ~ 240 DEG C, and soaking time is 6h ~ 48h.
9. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that step (6) is described
The feeding temperature of spray drying is 170 ~ 210 DEG C, and the spraying feed rate is 500-900mL/h.
10. the environment-friendly preparation method thereof of rich lithium tertiary cathode material according to claim 2, which is characterized in that in step (7),
The baking operation are as follows: by the persursor material after drying and grinding in the 400-550 DEG C of pre-sintering 4-6h in air atmosphere, so
After be cooled to room temperature and ground, be finally warming up to 800-950 DEG C of roasting 8-16h, cooled to room temperature.
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| CN110176590A (en) * | 2019-05-31 | 2019-08-27 | 淮安新能源材料技术研究院 | The rich lithium presoma of spherical shape that be made of class square and its made of lithium-rich anode material and product preparation method |
| CN110350164A (en) * | 2019-06-24 | 2019-10-18 | 湖南省正源储能材料与器件研究所 | A kind of compound nickelic tertiary cathode material of multiphase and preparation method thereof |
| CN111675249A (en) * | 2020-06-11 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of copper-loaded ternary nanobelt cathode material, product and application thereof |
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