CN108793268A - Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof - Google Patents
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof Download PDFInfo
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Abstract
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof, the ternary anode material precursor are the core-shell structure particles of 4~12 μm of average grain diameter；Wherein, kernel is that the hydroxide of nickel cobalt manganese precipitates, shell is the carbonate deposition of nickel cobalt manganese, and nickel content is continuously decreased from the center of core-shell structure particles to shell layer surface, manganese content gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is uniformly distributed at the center of core-shell structure particles with shell.The invention also discloses the preparation methods of the ternary anode material precursor.The tertiary cathode material that ternary anode material precursor of the present invention is mixed after lithium calcining is assembled into battery, under 0.1C, discharge capacity is up to 198mAh/g for the first time, 100 circle of cycle, remains at 182mAh/g, and under 5C, specific discharge capacity is up to 176.3mAh/g；The method of the present invention is simple for process, it is at low cost, be suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of nickel-cobalt-manganternary ternary anode material presomas and preparation method thereof, and in particular to a kind of nucleocapsid knot
Structure gradient nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof.
Background technology
As science and technology rapidly develops, the electronic products such as smart mobile phone, laptop and New-energy electric vehicle
It is universal, to lithium ion battery, more stringent requirements are proposed.Ternary material as one kind in anode material for lithium-ion batteries, by
, specific capacity high, of low cost the advantages that high in its voltage, be generally acknowledged most promising anode material for lithium-ion batteries it
One.
In order to obtain higher energy density, ternary material mainly uses two methods at present, prepares sphere material and height
Nickel content material.But high-nickel material is in actual use, cycle and high rate performance are relatively poor, how to prepare height ratio capacity
Ternary material become one of research emphasis.
CN105870414A discloses a kind of preparation method of nickel-cobalt-manganese ternary material, is the sulfuric acid using nickel, cobalt, manganese
Salt, using sodium hydroxide as precipitating reagent, ammonium hydroxide is complexing agent, and nickel-cobalt-manganese ternary material precursor is prepared by co-precipitation.But
When mixed lithium calcining prepares positive ternary material, preroast is needed, mechanical activation, process is complex.
CN106058238A discloses a kind of preparation method of nickel-cobalt-manganese ternary material, be using nickel, cobalt, manganese it is solvable
Salt, hydroxide are precipitating reagent, prepare nickel-cobalt-manganese ternary material precursor by co-precipitation, then using lithium carbonate, magnesium acetate, fluorine
Change the sintering of lithium ball milling.Although this method prepares tertiary cathode material using coprecipitation method, and is adulterated using fluorine, magnesium, cycle and
High rate performance gets a promotion, and still, synthesis technology is complex.
CN103700845A discloses a kind of preparation method of nickel-cobalt-manganese ternary material, by configuring three kinds of various concentrations
Manganese sulfate, nickel sulfate, cobalt sulfate solution, and three kinds of various concentrations of configuration sodium hydroxide and ammonia spirit, using different
Charging sequence prepares gradient anode ternary material.But gained ternary material specific capacity is low, only has 150mAh/g at 5C.
CN102637866A discloses a kind of preparation method of the anode material for lithium-ion batteries with concentration gradient, is logical
Cross and spherical high-nickel material be distributed in the solution containing lithium nickel cobalt manganese using suitable dispersant, then with spray drying method system
The standby presoma with nucleocapsid, and combine calcinating system appropriate makes the nickel element of presoma stratum nucleare to shell divergent contour
At one layer of concentration gradient layer.But this method needs the method that co-precipitation and spray drying is respectively adopted, preparation process is complicated,
And resulting materials specific capacity at 2C only has 169mAh/g.
Invention content
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of electric discharge ratio
The nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of capacity height, cycle and good rate capability.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of work
The preparation side of skill nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma that is simple, at low cost, being suitable for industrialized production
Method.
The technical solution adopted by the present invention to solve the technical problems is as follows：Nucleocapsid gradient nickel-cobalt-manganese ternary anode material
Material precursor, the ternary anode material precursor are the core-shell structure particles of 4~12 μm of average grain diameter；Wherein, kernel is nickel
The hydroxide of cobalt manganese precipitates, and shell is the carbonate deposition of nickel cobalt manganese, and nickel content is from the center of core-shell structure particles to shell
Layer surface continuously decreases, and manganese content gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is in nucleocapsid knot
The center of structure particle is uniformly distributed with shell.The structure of the concentration gradient can improve the cycle and high rate performance of material, interior
Core is that the hydroxide of nickel cobalt manganese precipitates, and compact structure, shell is the carbonate deposition of nickel cobalt manganese, is more likely formed after high temperature sintering
Micropore is conducive to mixed lithium and fully react diffusion with lithium ion in charge and discharge process.The low manganese of kernel is nickelic can to ensure charge and discharge
Capacity, shell low nickel and high manganese can ensure charge and discharge cycles and high rate performance.
Preferably, the average diameter of the kernel is 3~9 μm, and the average thickness of shell is 1~4 μm.
Preferably, the micropore that the shell is 0.1~0.5 μm with aperture.
The ternary anode material precursor can be applied to anode material for lithium-ion batteries production field.It is preferred that by the core
Shell structure gradient nickel-cobalt-manganternary ternary anode material presoma carries out mixed lithium sintering, and specific method is：By lithium and the nucleocapsid
Gradient nickel-cobalt-manganternary ternary anode material presoma, with lithium and nickel, cobalt, manganese element summation molar ratio for 1.01~1.08:1 ratio
Example first at 400~500 DEG C, is pre-sintered 2~8h after mixing, then at 650~800 DEG C, is sintered 8~16h, obtain lithium from
Sub- cell positive material.
Technical solution is used by the present invention further solves its technical problem：Nucleocapsid gradient nickel-cobalt-manganese ternary is just
The preparation method of pole material precursor, includes the following steps：
（1）Low nickel content nickel cobalt manganese solution is pumped into the container equipped with high nickel content nickel cobalt or nickel cobalt manganese solution, and is stirred, with
The high nickel content nickel cobalt for being constantly pumped into low nickel content nickel cobalt manganese solution or nickel cobalt manganese solution are pumped into equipped with ammonia spirit by this simultaneously
Reaction kettle in, and simultaneously with ammonium hydroxide adjust reaction system ammonia concn, with hydroxide precipitant solution adjust reactant
The pH value of system, stirring carry out coprecipitation reaction obtain presoma nuclear material until mean particle size grows to 3~9 μm, continue into
Hydroxide precipitant solution is only replaced with pH of the carbonate deposition agent solution for adjusting reaction system by row aforesaid operations
Value, stirring carries out coprecipitation reaction, until low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution finish,
Obtain the solution containing presoma nucleocapsid layer material；
（2）By step（1）Solution stirring of the gained containing presoma nucleocapsid layer material is aged, and is filtered, is washed, dry, is obtained
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma.
Preferably, step（1）In, the charging rate of the low nickel content nickel cobalt manganese solution is 20~60mL/h, described mixed
The charging rate for closing solution is 50~100mL/h.The charging rate is too fast or can all influence the equal of Material growth speed slowly excessively
Even property.
Preferably, step（1）In, in the low nickel content nickel cobalt manganese solution, a concentration of 1~3mol/L of metal ion,
The molar percentage that Ni accounts for total metal ion is that the molar percentage that 40~70%, Co accounts for total metal ion is that 10~40%, Mn is accounted for
The molar percentage of total metal ion is 20~50%, and Ni, Co, Mn ion summation are 100%.It is more advantageous to life under the ratio
At nickel, the low nickel Shell Materials of manganese graded.
Preferably, step（1）In, in the high nickel content nickel cobalt or nickel cobalt manganese solution, metal ion a concentration of 1~
The molar percentage that 3mol/L, Ni account for total metal ion be the molar percentage that 60~90%, Co accounts for total metal ion be 10~
The molar percentage that 40%, Mn account for total metal ion is 0~30%, and Ni, Co, Mn ion summation are 100%.Under the ratio more
Be conducive to generate nickel, manganese graded nickelic inner nuclear material.
Preferably, step（1）In, in same reaction system, the nickel content of low nickel content nickel cobalt manganese solution is less than nickelic
The nickel content of content nickel cobalt or nickel cobalt manganese solution.
Preferably, step（1）In, in reaction kettle ammonia spirit, low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or
The volume ratio of nickel cobalt manganese solution is 0.1~10:0.8~1.2:1（More preferable 0.5~2.5:0.8~1.2:1）.In the charging
Under ratio, it is more advantageous to the beginning of coprecipitation reaction and the control of material gradient.
Preferably, step（1）In, the molar concentration of the ammonia spirit is 0.3~0.5mol/L.Under the concentration,
It is more advantageous to control particle surface pattern.
Preferably, step（1）In, it adjusts reaction system ammonia concn with ammonium hydroxide and is maintained at 0.3~0.5mol/L.The present invention
The method that method uses acid solution titration, molar concentration of the detection ammonium hydroxide in entire reaction process reaction system, to control ammonia
The addition of water, to keep ammonia concn.It is more advantageous to the surface topography of control particle in the concentration.
Preferably, step（1）In, the mass concentration of the ammonium hydroxide is 25~28%.
Preferably, step（1）In, with hydroxide precipitant solution adjust pH value of reaction system be maintained at 10.5~
11.5.It is reacted under the pH value, it is ensured that particle growth rate will not be too fast or excessively slow.
Preferably, step（1）In, the molar concentration of the hydroxide precipitant solution is 5~10mol/L.
Preferably, step（1）In, the hydroxide precipitating reagent is in sodium hydroxide, potassium hydroxide or lithium hydroxide etc.
One or more.
Preferably, step（1）In, it adjusts pH value of reaction system with carbonate deposition agent solution and is maintained at 8.5~10.5.?
Under the pH value, it is ensured that particle growth rate will not be too fast or excessively slow.
Preferably, step（1）In, the molar concentration of the carbonate deposition agent solution is 0.5~1.5mol/L.
Preferably, step（1）In, the carbonate deposition agent is sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate or carbon
One or more of potassium hydrogen phthalate etc..
Preferably, step（1）In, the co-precipitation for generating presoma nuclear material and generating presoma nucleocapsid layer material is anti-
The speed of Ying Zhong, stirring are 600~1200r/min, and temperature is 50~70 DEG C.Under the mixing speed, it is more advantageous to
The formation of granule-morphology is more advantageous to the progress of reaction at said temperatures.
The present invention measures the mean particle size during generating presoma nuclear material using laser particle size analyzer, to sentence
Disconnected reaction end.
Preferably, step（1）In, the low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution are can
The mixed solution of insoluble nickel salt and soluble cobalt or soluble nickel salt, soluble cobalt and soluble manganese salt.
Preferably, the soluble nickel salt is one or more of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride etc..
Preferably, the soluble cobalt is one or more of cobaltous sulfate, cobalt nitrate, cobalt acetate or cobalt chloride etc..
Preferably, the soluble manganese salt is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride etc..
Preferably, step（2）In, the speed of the stirring is 400~800r/min.It is more advantageous in the mixing speed
The uniformity of granule-morphology.
Preferably, step（2）In, the temperature of the ageing is 50~80 DEG C, and the time is 5~15h.It is more advantageous by being aged
In the uniformity of granular grows.
Preferably, step（2）In, the temperature of the drying is 50~100 DEG C, and the time is 5~15h.If not in the temperature
It is all more easy to that side reaction occurs in degree and time range.
Beneficial effects of the present invention are as follows：
（1）Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the present invention is the nucleocapsid of 4~12 μm of average grain diameter
Particle, wherein kernel average diameter is 3~9 μm, and shell is average 1~3 μm thick, and kernel is fine and close, shell band micropore, and kernel is
The hydroxide of nickel cobalt manganese precipitates, and shell is the carbonate deposition of nickel cobalt manganese, and nickel content from the center of core-shell structure particles to
Shell layer surface continuously decreases, and manganese content gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is in nucleocapsid
The center of structure particles is uniformly distributed with shell；The nickelic high power capacity that can ensure ternary material of low manganese of kernel, shell it is low
The high manganese of nickel can ensure the cycle and high rate performance of ternary material；
（2）When nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the present invention carries out mixed lithium sintering, since kernel is fine and close,
Shell carries micropore, can not only ensure that mixed lithium sintering reaction is more complete, can also shorten the diffusion admittance of lithium ion, improve
The chemical property of tertiary cathode material；Tertiary cathode material after mixed lithium is calcined is assembled into battery, in 0.1C（17mA/g）
Current density under, discharge capacity may be up to 198mAh/g for the first time, in 5C（850mA/g）Current density under, specific discharge capacity
Up to 176.3mAh/g；Under 1C current densities, after 100 circle of cycle, specific discharge capacity remains at 182mAh/g.
（3）The method of the present invention is simple for process, it is at low cost, be suitable for industrialized production.
Description of the drawings
Fig. 1 is the XRD diagram of 1 gained nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the embodiment of the present invention；
Fig. 2 is the SEM figures of 1 gained nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the embodiment of the present invention；
Fig. 3 is that the focused ion beam of 1 gained nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the embodiment of the present invention is surveyed
Attempt；
Fig. 4 is 1 gained nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the embodiment of the present invention after mixed lithium sintering, institute
Charge and discharge cycles figure of the battery of assembling under different multiplying；
Fig. 5 is 1 gained nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the embodiment of the present invention after mixed lithium sintering, institute
Charge and discharge cycles figure of the battery of assembling at 1C；
Fig. 6 is the SEM figures of 2 gained nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of the embodiment of the present invention.
Specific implementation mode
With reference to embodiment and attached drawing, the invention will be further described.
The method that the embodiment of the present invention uses acid solution titration detects ammonium hydroxide rubbing in entire reaction process reaction system
That concentration；The embodiment of the present invention is averaged grain using the particle that laser particle size analyzer measures during generating presoma nuclear material
Diameter；Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma embodiment 1
The ternary anode material precursor is the core-shell structure particles of 10 μm of average grain diameter；Wherein, kernel is the hydrogen of nickel cobalt manganese
Oxide precipitation, shell be nickel cobalt manganese carbonate deposition, and nickel content from the center of core-shell structure particles to shell layer surface by
It gradually reduces, manganese content gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is in core-shell structure particles
Center is uniformly distributed with shell；The average diameter of the kernel is 8 μm, and the average thickness of shell is 2 μm；The shell carries hole
The micropore that diameter is 0.2~0.5 μm.
The preparation method embodiment 1 of nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma
（1）By 2L low nickel content nickel cobalt manganese solutions（The mixed solution of nickel sulfate, cobaltous sulfate and manganese sulfate, wherein Ni, Co, Mn are accounted for
The molar percentage of total metal ion is followed successively by 70%, 10%, 20%, concentration of metal ions 2mol/L）With charging rate 40mL/
H is pumped into equipped with 2L high nickel content nickel and cobalt solutions（The mixed solution of nickel sulfate and cobaltous sulfate, wherein Ni, Co account for total metal ion
Molar percentage be followed successively by 90%, 10%, concentration of metal ions 2mol/L）Container in, and stir, at the same time, will not
The disconnected high nickel content nickel and cobalt solution for being pumped into low nickel content nickel cobalt manganese solution is pumped into charging rate 80mL/h equipped with 2L, mole dense
Degree be 0.45mol/L ammonia spirit, volume be 5L reaction kettle in, and simultaneously use mass concentration 25% ammonium hydroxide adjust reaction
The ammonia concn of system is maintained at 0.45mol/L, and the pH value that reaction system is adjusted with the sodium hydroxide solution of 10mol/L is maintained at
11.4, at 1000r/min, 60 DEG C, stirring carries out coprecipitation reaction and obtains presoma core until mean particle size grows to 8 μm
Material continues aforesaid operations, and sodium hydroxide solution is only replaced with to the sodium carbonate liquor of 1mol/L for adjusting reactant
The pH value of system is maintained at 9.5, and at 1000r/min, 60 DEG C, stirring carries out coprecipitation reaction, until low nickel content nickel cobalt manganese solution
It is finished with the charging of high nickel content nickel and cobalt solution, obtains the solution containing presoma nucleocapsid layer material；
（2）By step（1）Solution of the gained containing presoma nucleocapsid layer material, at 600r/min, 60 DEG C, stirring is aged
10h, filtering, deionized water washing, at 80 DEG C, dry 10h obtains nucleocapsid gradient nickel-cobalt-manganternary ternary anode material forerunner
Body.
As shown in Figure 1, the ingredient of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma is the hydrogen of nickel cobalt manganese
The carbonate of oxide and nickel cobalt manganese, no dephasign generate.
As shown in Figure 2, the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma is the ball of 10 μm of average grain diameter
Forming core shell structure granules, and the micropore that shell is 0.2~0.5 μm with aperture, whole pattern are uniform.
From the figure 3, it may be seen that the average diameter of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma kernel is 8 μ
The average thickness of m, shell are 2 μm, wherein nickel content is continuously decreased from the center of core-shell structure particles to shell layer surface, and manganese contains
Amount gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is equal with shell at the center of core-shell structure particles
Even distribution.
Nucleocapsid nickel-cobalt-manganternary ternary anode material presoma described in the embodiment of the present invention is subjected to mixed lithium sintering, specific side
Method is：By lithium and the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma, with lithium and nickel, cobalt, manganese element summation
Molar ratio is 1.05:1 ratio first at 500 DEG C, is pre-sintered 4h, then at 750 DEG C, is sintered 12h, obtains lithium after mixing
Ion battery positive electrode.
Gained anode material for lithium-ion batteries is assembled into battery：Anode material for lithium-ion batteries obtained by 0.16 g is weighed,
Addition 0.02g acetylene blacks make conductive agent and 0.02g Kynoar makees binder, and N-Methyl pyrrolidone is mixed as dispersant
After closing uniformly, it is applied on aluminium foil and positive plate is made, in vacuum glove box, using metal lithium sheet as cathode, with the composite membrane of pe, pp
For diaphragm, 1mol/L lithium hexafluoro phosphates/DMC:EC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
As shown in Figure 4, in 2.5~4.3V voltage ranges, 0.1C（17mA/g）Current density under, discharge specific volume for the first time
Amount is 198mAh/g, 5C（850mA/g）Current density under, first discharge specific capacity 176.3mAh/g.
As shown in Figure 5, in 2.5~4.3V voltage ranges, 1C（170mA/g）Current density under, cycle 100 circle after,
Specific discharge capacity remains at 182mAh/g.
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma embodiment 2
The ternary anode material precursor is the core-shell structure particles of 12 μm of average grain diameter；Wherein, kernel is the hydrogen of nickel cobalt manganese
Oxide precipitation, shell be nickel cobalt manganese carbonate deposition, and nickel content from the center of core-shell structure particles to shell layer surface by
It gradually reduces, manganese content gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is in core-shell structure particles
Center is uniformly distributed with shell；The average diameter of the kernel is 9 μm, and the average thickness of shell is 3 μm；The shell carries hole
The micropore that diameter is 0.1~0.4 μm.
The preparation method embodiment 2 of nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma
（1）By 1.6L low nickel content nickel cobalt manganese solutions（The mixed solution of nickel nitrate, cobalt nitrate and manganese nitrate, wherein Ni, Co, Mn
The molar percentage for accounting for total metal ion is followed successively by 40%, 30%, 30%, concentration of metal ions 2.5mol/L）With charging rate
30mL/h is pumped into equipped with 2L high nickel content nickel cobalt manganese solutions（The mixed solution of nickel nitrate, cobalt nitrate and manganese nitrate, wherein Ni,
The molar percentage that Co, Mn account for total metal ion is followed successively by 80%, 10%, 10%, concentration of metal ions 2.5mol/L）Container
In, and stir, at the same time, the high nickel content nickel cobalt manganese solution of low nickel content nickel cobalt manganese solution will be constantly pumped into charging rate
60mL/h is pumped into equipped with 1.8L, the ammonia spirit that molar concentration is 0.4mol/L, and volume is and to be used simultaneously in the reaction kettle of 5L
The ammonia concn that the ammonium hydroxide of mass concentration 25% adjusts reaction system is maintained at 0.45mol/L, with the sodium hydroxide solution of 5mol/L
The pH value for adjusting reaction system is maintained at 11.0, and at 800r/min, 55 DEG C, stirring carries out coprecipitation reaction, until particle is average
Particle size growth obtains presoma nuclear material to 9 μm, continues aforesaid operations, sodium hydroxide solution is only replaced with 0.8mol/L
Sodium carbonate liquor adjust reaction system pH value be maintained at 9, at 800r/min, 55 DEG C, stirring carry out coprecipitation reaction, until
Low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt manganese solution finish, and obtain the solution containing presoma nucleocapsid layer material；
（2）By step（1）Solution of the gained containing presoma nucleocapsid layer material, at 500r/min, 70 DEG C, stirring is aged
12h, filtering, deionized water washing, at 60 DEG C, dry 8h obtains nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma.
After testing, the ingredient of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma is the hydroxide of nickel cobalt manganese
The carbonate of object and nickel cobalt manganese, no dephasign generate.
It will be appreciated from fig. 6 that the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma is the ball of 12 μm of average grain diameter
Forming core shell structure granules, and the micropore that shell is 0.1~0.4 μm with aperture, whole pattern are uniform.
After testing, the average diameter of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma kernel is 9 μm, shell
Layer average thickness be 3 μm, wherein nickel content is continuously decreased from the center of core-shell structure particles to shell layer surface, manganese content from
The center of core-shell structure particles to shell layer surface gradually rises, and the content of cobalt is uniformly divided at the center of core-shell structure particles with shell
Cloth.
Nucleocapsid nickel-cobalt-manganternary ternary anode material presoma described in the embodiment of the present invention is subjected to mixed lithium sintering, specific side
Method is：By lithium and the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma, with lithium and nickel, cobalt, manganese element summation
Molar ratio is 1.06:1 ratio first at 450 DEG C, is pre-sintered 5h, then at 700 DEG C, is sintered 10h, obtains lithium after mixing
Ion battery positive electrode.
Gained anode material for lithium-ion batteries is assembled into battery：Anode material for lithium-ion batteries obtained by 0.16 g is weighed,
Addition 0.02g acetylene blacks make conductive agent and 0.02g Kynoar makees binder, and N-Methyl pyrrolidone is mixed as dispersant
After closing uniformly, it is applied on aluminium foil and positive plate is made, in vacuum glove box, using metal lithium sheet as cathode, with the composite membrane of pe, pp
For diaphragm, 1mol/L lithium hexafluoro phosphates/DMC:EC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
After testing, in 2.5~4.3V voltage ranges, 0.1C（17mA/g）Current density under, first discharge specific capacity
For 182mAh/g, 5C（850mA/g）Current density under, first discharge specific capacity 162.3mAh/g.
After testing, in 2.5~4.3V voltage ranges, 1C（170mA/g）Current density under, cycle 100 circle after, electric discharge
Specific capacity remains at 174mAh/g.
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma embodiment 3
The ternary anode material precursor is the core-shell structure particles of 11 μm of average grain diameter；Wherein, kernel is the hydrogen of nickel cobalt manganese
Oxide precipitation, shell be nickel cobalt manganese carbonate deposition, and nickel content from the center of core-shell structure particles to shell layer surface by
It gradually reduces, manganese content gradually rises from the center of core-shell structure particles to shell layer surface, and the content of cobalt is in core-shell structure particles
Center is uniformly distributed with shell；The average diameter of the kernel is 7 μm, and the average thickness of shell is 4 μm；The shell carries hole
The micropore that diameter is 0.1~0.5 μm.
The preparation method embodiment 3 of nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma
（1）By 2.4L low nickel content nickel cobalt manganese solutions（The mixed solution of nickel chloride, cobalt chloride and manganese chloride, wherein Ni, Co, Mn
The molar percentage for accounting for total metal ion is followed successively by 40%, 20%, 40%, concentration of metal ions 1.5mol/L）With charging rate
50mL/h is pumped into equipped with 2L high nickel content nickel cobalt manganese solutions（The mixed solution of nickel chloride, cobalt chloride and manganese chloride, wherein Ni,
The molar percentage that Co, Mn account for total metal ion is followed successively by 60%, 20%, 20%, concentration of metal ions 1.5mol/L）Container
In, and stir, at the same time, the high nickel content nickel cobalt manganese solution of low nickel content nickel cobalt manganese solution will be constantly pumped into charging rate
100mL/h is pumped into equipped with 2.2L, the ammonia spirit that molar concentration is 0.4mol/L, and volume is and to be used simultaneously in the reaction kettle of 5L
The ammonia concn that the ammonium hydroxide of mass concentration 28% adjusts reaction system is maintained at 0.40mol/L, with the potassium hydroxide solution of 5mol/L
The pH value for adjusting reaction system is maintained at 11.0, and at 700r/min, 65 DEG C, stirring carries out coprecipitation reaction, until particle is average
Particle size growth obtains presoma nuclear material to 7 μm, continues aforesaid operations, sodium hydroxide solution is only replaced with 1.2mol/L
Solution of potassium carbonate adjust reaction system pH value be maintained at 9, at 700r/min, 65 DEG C, stirring carry out coprecipitation reaction, until
Low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt manganese solution finish, and obtain the solution containing presoma nucleocapsid layer material；
（2）By step（1）Solution of the gained containing presoma nucleocapsid layer material, at 700r/min, 50 DEG C, stirring is aged
8h, filtering, deionized water washing, at 100 DEG C, dry 12h obtains nucleocapsid gradient nickel-cobalt-manganternary ternary anode material forerunner
Body.
After testing, the ingredient of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma is the hydroxide of nickel cobalt manganese
The carbonate of object and nickel cobalt manganese, no dephasign generate.
After testing, the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma is the spherical nuclei of 11 μm of average grain diameter
Shell structure granules, and the micropore that shell is 0.1~0.5 μm with aperture, whole pattern are uniform.
After testing, the average diameter of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma kernel is 7 μm, shell
Layer average thickness be 4 μm, wherein nickel content is continuously decreased from the center of core-shell structure particles to shell layer surface, manganese content from
The center of core-shell structure particles to shell layer surface gradually rises, and the content of cobalt is uniformly divided at the center of core-shell structure particles with shell
Cloth.
Nucleocapsid nickel-cobalt-manganternary ternary anode material presoma described in the embodiment of the present invention is subjected to mixed lithium sintering, specific side
Method is：By lithium and the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma, with lithium and nickel, cobalt, manganese element summation
Molar ratio is 1.04:1 ratio first at 500 DEG C, is pre-sintered 6h, then at 800 DEG C, is sintered 9h, obtains lithium after mixing
Ion battery positive electrode.
Gained anode material for lithium-ion batteries is assembled into battery：Anode material for lithium-ion batteries obtained by 0.16 g is weighed,
Addition 0.02g acetylene blacks make conductive agent and 0.02g Kynoar makees binder, and N-Methyl pyrrolidone is mixed as dispersant
After closing uniformly, it is applied on aluminium foil and positive plate is made, in vacuum glove box, using metal lithium sheet as cathode, with the composite membrane of pe, pp
For diaphragm, 1mol/L lithium hexafluoro phosphates/DMC:EC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
After testing, in 2.5~4.3V voltage ranges, 0.1C（17mA/g）Current density under, first discharge specific capacity
For 174mAh/g, 5C（850mA/g）Current density under, first discharge specific capacity 156.1mAh/g.
After testing, in 2.5~4.3V voltage ranges, 1C（170mA/g）Current density under, cycle 100 circle after, electric discharge
Specific capacity remains at 165.1mAh/g.
Claims (10)
1. a kind of nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma, it is characterised in that：Before the tertiary cathode material
Drive the core-shell structure particles that body is 4~12 μm of average grain diameter；Wherein, kernel is that the hydroxide of nickel cobalt manganese precipitates, and shell is nickel
The carbonate deposition of cobalt manganese, and nickel content is continuously decreased from the center of core-shell structure particles to shell layer surface, manganese content is from nucleocapsid
The center of structure particles to shell layer surface gradually rises, and the content of cobalt is uniformly distributed at the center of core-shell structure particles with shell.
2. nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma according to claim 1, it is characterised in that：In described
The average diameter of core is 3~9 μm, and the average thickness of shell is 1~4 μm；The shell is 0.1~0.5 μm micro- with aperture
Hole.
3. a kind of preparation method of nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma as claimed in claim 1 or 2,
It is characterized in that, includes the following steps：
（1）Low nickel content nickel cobalt manganese solution is pumped into the container equipped with high nickel content nickel cobalt or nickel cobalt manganese solution, and is stirred, with
The high nickel content nickel cobalt for being constantly pumped into low nickel content nickel cobalt manganese solution or nickel cobalt manganese solution are pumped into equipped with ammonia spirit by this simultaneously
Reaction kettle in, and simultaneously with ammonium hydroxide adjust reaction system ammonia concn, with hydroxide precipitant solution adjust reactant
The pH value of system, stirring carry out coprecipitation reaction obtain presoma nuclear material until mean particle size grows to 3~9 μm, continue into
Hydroxide precipitant solution is only replaced with pH of the carbonate deposition agent solution for adjusting reaction system by row aforesaid operations
Value, stirring carries out coprecipitation reaction, until low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution finish,
Obtain the solution containing presoma nucleocapsid layer material；
（2）By step（1）Solution stirring of the gained containing presoma nucleocapsid layer material is aged, and is filtered, is washed, dry, is obtained
Nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma.
4. the preparation method of nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma according to claim 3, feature
It is：Step（1）In, the charging rate of the low nickel content nickel cobalt manganese solution is 20~60mL/h, and the mixed solution adds
Material speed is 50~100mL/h；In the low nickel content nickel cobalt manganese solution, a concentration of 1~3mol/L of metal ion, Ni are accounted for always
The molar percentage of metal ion is that the molar percentage that 40~70%, Co accounts for total metal ion is that 10~40%, Mn accounts for total metal
The molar percentage of ion is 20~50%, and Ni, Co, Mn ion summation are 100%；The high nickel content nickel cobalt or nickel cobalt manganese solution
In, a concentration of 1~3mol/L of metal ion, Ni account for total metal ion molar percentage be 60~90%, Co account for total metal from
It is 0~30% that the molar percentage of son, which is the molar percentage that 10~40%, Mn accounts for total metal ion, and Ni, Co, Mn ion summation are
100%；In same reaction system, the nickel content of low nickel content nickel cobalt manganese solution is less than high nickel content nickel cobalt or nickel cobalt manganese solution
Nickel content.
5. special according to the preparation method of the nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma of claim 3 or 4
Sign is：Step（1）In, ammonia spirit, low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese are molten in reaction kettle
The volume ratio of liquid is 0.1~10:0.8~1.2:1；The molar concentration of the ammonia spirit is 0.3~0.5mol/L；With ammonium hydroxide tune
Section reaction system ammonia concn is maintained at 0.3~0.5mol/L；The mass concentration of the ammonium hydroxide is 25~28%.
6. according to the preparation method of one of claim 3~5 nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma,
It is characterized in that：Step（1）In, it adjusts pH value of reaction system with hydroxide precipitant solution and is maintained at 10.5~11.5；Institute
The molar concentration for stating hydroxide precipitant solution is 5~10mol/L；The hydroxide precipitating reagent is sodium hydroxide, hydrogen-oxygen
Change one or more of potassium or lithium hydroxide.
7. according to the preparation method of one of claim 3~6 nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma,
It is characterized in that：Step（1）In, it adjusts pH value of reaction system with carbonate deposition agent solution and is maintained at 8.5~10.5；The carbon
The molar concentration of hydrochlorate precipitant solution is 0.5~1.5mol/L；The carbonate deposition agent is sodium carbonate, potassium carbonate, carbonic acid
One or more of lithium, sodium bicarbonate or saleratus.
8. according to the preparation method of one of claim 3~7 nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma,
It is characterized in that：Step（1）In, the coprecipitation reaction for generating presoma nuclear material and generating presoma nucleocapsid layer material
In, the speed of stirring is 600~1200r/min, and temperature is 50~70 DEG C.
9. according to the preparation method of one of claim 3~8 nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma,
It is characterized in that：Step（1）In, the low nickel content nickel cobalt manganese solution and high nickel content nickel cobalt or nickel cobalt manganese solution are solubility
The mixed solution of nickel salt and soluble cobalt or soluble nickel salt, soluble cobalt and soluble manganese salt；The soluble nickel salt
For one or more of nickel sulfate, nickel nitrate, nickel acetate or nickel chloride；The soluble cobalt is cobaltous sulfate, cobalt nitrate, second
One or more of sour cobalt or cobalt chloride；The solubility manganese salt is one in manganese sulfate, manganese nitrate, manganese acetate or manganese chloride
Kind is several.
10. according to the preparation side of one of claim 3~9 nucleocapsid gradient nickel-cobalt-manganternary ternary anode material presoma
Method, it is characterised in that：Step（2）In, the speed of the stirring is 400~800r/min；The temperature of the ageing is 50~80
DEG C, the time is 5~15h；The temperature of the drying is 50~100 DEG C, and the time is 5~15h.
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