A kind of high magnification doping type nickel-cobalt-manganese ternary material and preparation method thereof
阅读说明：本技术 一种高倍率掺杂型镍钴锰三元材料及其制备方法 (A kind of high magnification doping type nickel-cobalt-manganese ternary material and preparation method thereof ) 是由 翁雅青 王爽 徐志峰 胡银 李玲 晏南富 崔红敏 曹才放 于 2019-09-16 设计创作，主要内容包括：本发明提供一种高倍率掺杂型镍钴锰三元材料Li(Ni<Sub>x</Sub>Co<Sub>y</Sub>Mn<Sub>z</Sub>)<Sub>l-n</Sub>M<Sub>n</Sub>O<Sub>2</Sub>及其制备方法,该制备方法为：将镍钴锰以及掺杂元素M的金属盐溶液与由沉淀剂和络合剂组成的混合溶液并流加料,得到沉淀产物后进行煅烧,分解后的过渡金属复合氧化物与锂盐充分混合,最后高温下焙烧得到Li(Ni<Sub>x</Sub>Co<Sub>y</Sub>Mn<Sub>z</Sub>)<Sub>l-n</Sub>M<Sub>n</Sub>O<Sub>2</Sub>。该方法得到的材料组分分布更加均匀,形貌和粒度可控,层状结构稳定、循环性能良好,由于在三元前驱体制备过程中掺入了改进杂质离子,改善了材料的倍率性能,且掺杂元素存在的最佳含量区间还可以反馈到失效锂电池材料的净化工艺中,为适当放宽除杂深度,节约回收成本提供决策依据。(The present invention provides a kind of high magnification doping type nickel-cobalt-manganese ternary material Li (Ni x Co y Mn z ) l‑n M n O 2 And preparation method thereof, this is the preparation method comprises the following steps: the mixed solution cocurrent adding material formed by the metal salt solution of nickel cobalt manganese and doped chemical M and by precipitating reagent and complexing agent, it is calcined after obtaining precipitated product, compound transition metal oxide after decomposition is sufficiently mixed with lithium salts, and roasting obtains Li (Ni under final high temperature x Co y Mn z ) l‑n M n O 2 .The material component distribution that this method obtains is more uniform, pattern and granularity are controllable, layer structure is stable, cycle performance is good, due to being mixed with improvement foreign ion in ternary precursor preparation process, improve the high rate performance of material, and optimum content section existing for doped chemical can also be fed back in the purification process of failure lithium battery material, suitably to relax removal of impurities depth, saved cost recovery and provided decision-making foundation.)
1. a kind of high magnification doping type nickel-cobalt-manganese ternary material Li (NixCoyMnz)l-nMnO2Preparation method, wherein M be doping Element, which is characterized in that the described method comprises the following steps:
1) ternary precursor is prepared
The content for adjusting nickel, cobalt, manganese and doped chemical in solution of metal sulfates, makes its molar ratio meet chemical formula Li (NixCoyMnz)l-nMnO2, wherein one in 0 < x < l, 0 < y < 1,0 < z < 1,0≤n≤0.1 and x+y+z=1, M Al, Mg, Cu Kind is a variety of, and the metal sulfate is passed through co-deposition process synthesis of ternary presoma；
2) calcining and decomposing
The ternary precursor is subjected to calcining and decomposing, obtains compound transition metal oxide；
3) high-temperature roasting
After mixing by the composite oxides and lithium source, roasting obtains a series of positive electrode Li under high temperature (NixCoyMnz)l-nMnO2。
2. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 1xCoyMnz)1-nMnO2Preparation side Method, which is characterized in that the chemical formula Li (NixCoyMnz)l-nMnO2Middle n=0.00125~0.1.
3. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 1xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that the step 1) includes:
The sulfate of the sulfate of nickel, the sulfate of cobalt, the sulfate of manganese and doped chemical is pressed into chemical general formula Li (NixCoyMnz)l-nMnO2Metering proportion ingredient, be added deionized water mixed；
Mixed solution, precipitating reagent and complexing agent are added in reaction vessel using peristaltic pump cocurrent, wherein complexing agent is ammonium hydroxide Solution, and it is passed through inert gas, it is uniformly mixed using electric blender, controls the technological parameter of reaction process to control precipitating The pattern and granularity of product, the technological parameter include reaction temperature, pH value, charging rate, material concentration, mixing speed, stir Mix time and digestion time；
In vacuum oven after sediment after reaction is repeatedly washed using deionized water, ternary precursor is obtained.
4. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 3xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that the solution of metal sulfates concentration of the mixed solution is 1.0~4.0molL-1, the precipitating reagent is NaOH or Na2CO3, the complexing agent concentration is 2.0~12.0gL-1。
5. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 3xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that the inert gas is at least one of nitrogen, argon gas, and flow is 1~10mlmin-1。
6. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 3xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that in the step 1), pH value control is 7.5~12, and reaction temperature is 35~65 DEG C, mixing speed 600 ~1500rmin-1, mixing time is 24~48h, and digestion time is 5~12h.
7. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 3xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that in the step 1) vacuum oven be specially at 60~120 DEG C be dried in vacuo 12h~ 36h。
8. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 1xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that lithium source in the step 3) is lithium hydroxide or lithium carbonate, and elemental lithium and described multiple in the lithium source The ratio between the total material amount for closing nickel in oxide, cobalt, manganese and doped chemical is 1.0-1.10.
9. high magnification doping type nickel-cobalt-manganese ternary material Li (Ni according to claim 1xCoyMnz)l-nMnO2Preparation side Method, which is characterized in that in the step 2), calcination temperature is 300~600 DEG C, and the reaction time is 3~10h；The step 3) In, high-temperature roasting temperature is 750~950 DEG C, and the reaction time is 10~20h.
10. a kind of high magnification doping type nickel-cobalt-manganese ternary material Li (NixCoyMnz)l-nMnO2, which is characterized in that the high magnification Doping type nickel-cobalt-manganese ternary material is made using preparation method as claimed in any one of claims 1-9 wherein.
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of high magnification doping type nickel-cobalt-manganese ternary material Li (NixCoyMnz)l-nMnO2And preparation method thereof.
Background technique
The principal element of restricting current new-energy automobile market is that power battery cost is excessively high and cruising ability is insufficient.Cause This, developing cheap efficient battery is to realize the commercialized most important thing of electric vehicle.In power battery field, generally adopt at present Anode material for lithium-ion batteries is ternary material and LiFePO 4 material.As electric car requires not course continuation mileage Disconnected to be promoted, the higher ternary material of energy density is increasingly becoming the main flow direction of power battery development, and the market share is increasing. But its own the shortcomings that, such as with high costs, cyclical stability and high rate performance difference still restrict the reality of ternary material Using.Therefore, reducing cobalt content to ensure that the structure of positive electrode and performance are stablized simultaneously is also the one of layered cathode material research and development A important content.
It is limited and the restriction of structural stability by anode material of lithium battery theoretical specific capacity, in practical industrial application In, it is contemplated that the problems such as cost is with promoting improves positive electrode specific energy, and compare practicable is exactly active development anode material Material efficiently synthesizes technology, studies the control principle of preparation process.
Summary of the invention
The main object of the present invention is to provide a kind of high magnification doping type nickel-cobalt-manganese ternary material Li (NixCoyMnz)l-nMnO2 And preparation method thereof, it is intended to solve the problems, such as that nickel-cobalt-manganese ternary material preparation cost is high, chemical property is bad.
To achieve the goals above, a kind of high magnification doping type nickel-cobalt-manganese ternary material Li provided by the invention (NixCoyMnz)l-nMnO2Preparation method, wherein M is doped chemical, method includes the following steps:
1) ternary precursor is prepared
The content for adjusting nickel, cobalt, manganese and doped chemical in solution of metal sulfates, makes its molar ratio meet chemical formula Li (NixCoyMnz)l-nMnO2, wherein one in 0 < x < l, 0 < y < 1,0 < z < 1,0≤n≤0.1 and x+y+z=1, M Al, Mg, Cu Kind is a variety of, and the metal sulfate is passed through co-deposition process synthesis of ternary presoma；
2) calcining and decomposing
The ternary precursor is subjected to calcining and decomposing, obtains compound transition metal oxide；
3) high-temperature roasting
After mixing by the composite oxides and lithium source, roasting obtains a series of positive electrode Li under high temperature (NixCoyMnz)l-nMnO2。
Preferably, the chemical formula Li (NixCoyMnz)l-nMnO2Middle n=0.00125~0.1.
Preferably, the step 1) includes:
The sulfate of the sulfate of nickel, the sulfate of cobalt, the sulfate of manganese and doped chemical is pressed into chemical general formula Li (NixCoyMnz)l-nMnO2Metering proportion ingredient, be added deionized water mixed；
Mixed solution, precipitating reagent and complexing agent are added in reaction vessel using peristaltic pump cocurrent, wherein complexing agent is Ammonia spirit, and it is passed through inert gas, it is uniformly mixed using electric blender, controls the technological parameter of reaction process to control The pattern and granularity of precipitated product, the technological parameter include reaction temperature, pH value, charging rate, material concentration, stirring speed Degree, mixing time and digestion time；
In vacuum oven after sediment after reaction is repeatedly washed using deionized water, ternary forerunner is obtained Body.
Preferably, the solution of metal sulfates concentration of the mixed solution is 1.0~4.0molL-1, the precipitating reagent is NaOH or Na2CO3, the complexing agent concentration is 2.0~12.0gL-1。
Preferably, the inert gas is at least one of nitrogen, argon gas, and flow is 1~10mlmin-1。
Preferably, in the step 1), pH value control is 7.5~12, and reaction temperature is 35~65 DEG C, and mixing speed is 600~1500rmin-1, mixing time is 24~48h, and digestion time is 5~12h.
Preferably, in the step 1) vacuum oven be specially at 60~120 DEG C be dried in vacuo 12h~ 36h。
Preferably, the lithium source in the step 3) is lithium hydroxide or lithium carbonate, and elemental lithium and described in the lithium source The ratio between nickel, cobalt, manganese and total material amount of doped chemical are 1.0-1.10 in composite oxides.
Preferably, in the step 2), calcination temperature is 300~600 DEG C, and the reaction time is 3~10h；The step 3) In, high-temperature roasting temperature is 750~950 DEG C, and the reaction time is 10~20h.
To achieve the goals above, high magnification doping type nickel-cobalt-manganese ternary material provided by the invention is used as any of the above-described Preparation method described in is made.
Technical concept of the invention is as follows:
Ternary material LiNi1/3Co1/3Mn1/3O2Preparation method mainly have high temperature solid-state method, coprecipitation, collosol and gel Method, spray pyrolysis, alloy electrolysis etc..Conventional high-temperature producing method, it is easy to operate, it is suitble to industrial production, but reactant Unevenness is mixed, solid phase reaction temperature is high, and production energy consumption is high, product grains size is larger, particle is uneven, causes product comprehensive It can not be high；In order to improve the mixability of source metal and lithium source presoma, sol-gel, co-precipitation, spray drying are developed The methods of, the materials chemistry homogeneity of soft chemical method preparation is good, chemical property is good, can suitably reduce solid phase reaction temperature, subtract Little crystallite size, but technical process control is complicated, product density decline.Wherein, coprecipitation mainly has hydroxide co-precipitation With two kinds of carbonate coprecipitation.In hydroxide co-precipitation, Mn is not only with Mn (OH)2Form precipitating, can also partial oxidation At Mn3+、Mn4+, with MnOOH or MnO2Form be precipitated out, so need synthesize precursor product under inert protective atmosphere. And Mn in carbonate solution with Mn2+In the presence of very stable, there is no be oxidized.Carbonate co-precipitation is in neutral item The good target material of pattern can be prepared under part, and requirement of the hydroxide coprecipitation step to solution acidity is very high.
Doping is to be commonly used in a kind of means for improving anode material of lithium battery, such as can further decrease ternary material Expect the dependence to Co element, reduce material preparation technology cost, while improving the cyclical stability of material, improving large current density Electrical property and structural stability etc..And on the other hand, foreign ion seriously affects recycling product during lithium battery circular regeneration Economic value and removal of impurities cost are high certainly will to hinder closed circulation, therefore, emphasis is answered to consider that plurality of impurity ions coexists pair The combined influence of positive electrode chemical property constructs flexible regulating strategy to reduce removal of impurities cost, provides simplification and follow The new approaches of circulation journey.
The present invention at least exists following the utility model has the advantages that 1, co-precipitation positive electrode material precursor component distribution obtained is more equal Even, precipitate particles are tiny, are suitble to large-scale production；2, prepare doping M element nickel cobalt manganese anode material be spherical morphology, Granule size is controllable, layer structure is stable, well especially high rate capability is greatly improved cycle performance；3, high magnification Doping type tertiary cathode material and preparation method thereof provides new thinking to simplify failure lithium battery circular regeneration process.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the XRD diagram of product prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figure of product prepared by the embodiment of the present invention 1；
Fig. 3 is the particle size distribution curve of product prepared by the embodiment of the present invention 1；
Fig. 4 is the first charge-discharge curve graph of product prepared by the embodiment of the present invention 1；
Fig. 5 is the cycle performance curve graph of the product of the preparation of the embodiment of the present invention 1 at room temperature；
Fig. 6 is the XRD diagram of product prepared by the embodiment of the present invention 2；
Fig. 7 is the high rate performance curve graph of product prepared by the embodiment of the present invention 2；
Fig. 8 is the first charge-discharge curve graph of product prepared by the embodiment of the present invention 3；
Fig. 9 is the SEM figure of product prepared by the embodiment of the present invention 4.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
In present embodiment: utilizing the X-ray diffraction of Japanese Shimadzu Corporation model MAXima_X XRD-7000 type The Crystal Structure that instrument carries out sample, test condition are as follows: Cu target K ray, pipe press 40KV, tube current 30mA, sweep speed For 4 ° of min-1, step-length is 0.02 °, and scanning range is 10 °~80 °；Electricity is scanned using the Quanta650FEG of FEI Co.'s production Sub- microscope carries out microscopic appearance characterization to sample；It is examined using CT-4008-5V6A-S1 (the new prestige in Shenzhen) 5V/20mA battery performance First charge-discharge and cycle performance test curve figure that instrument carries out battery are surveyed, is tested at room temperature.It is no longer superfluous in embodiment It states.
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