CN110416540A - A kind of nickelic tertiary cathode material and preparation method thereof - Google Patents
A kind of nickelic tertiary cathode material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of nickelic tertiary cathode material and preparation method thereof, and the method includes the steps 1, by nickelic ternary metal salt and nano-cellulose fiber, ultrasonic disperse is uniformly stood afterwards in deionized water, obtains mixed system A；Step 2, by mixed system A in conjunction with precipitating reagent, the presoma of nickelic tertiary cathode material is prepared with hydro-thermal method or coprecipitation；Step 3, the presoma of nickelic tertiary cathode material is uniformly mixed with lithium source, under oxygen atmosphere 600~900 DEG C calcining 8~for 24 hours, obtain nickelic tertiary cathode material；Nickelic tertiary cathode material of the invention is compared with the nickelic tertiary cathode material that nano-cellulose fiber is not added, electrochemical impedance is substantially reduced, cycle performance is obviously improved, and can improve the specific capacity of lithium ion battery to a certain extent, has preferable stability in constant temperature charge-discharge test.
Description
Technical field
The present invention relates to technical field of lithium ion battery positive pole material preparation, specially a kind of nickelic tertiary cathode material and
Preparation method.
Background technique
The rapid development in New-energy electric vehicle market proposes higher challenge to power lithium-ion battery system.Lithium ion
In battery system, the capacity and cycle performance of positive electrode largely limit the energy density of full battery and use the longevity
Life.Traditional lithium cobaltate cathode material and lithium iron phosphate positive material, nickelic ternary material are compared, abbreviation NCM811 has Gao Li
By potential advantages such as capacity, low cost and high voltages, it is the research hotspot of current field of lithium ion battery anode, has non-
The market potential of Chang Guang.
The particle of nickelic tertiary cathode material is usually that the primary particle of several nano-scales is aggregated and combination forms
Micron-sized second particle.In nickelic tertiary cathode material particle during charging and discharging, electrolyte and the particle surface
Side reaction strongly limit the capacity and cycle performance of nickelic tertiary cathode material, it is therefore desirable to by improving nickelic ternary just
The conjugation of pole material primary particle lowers the degrees of exposure of particle surface and electrolyte.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of nickelic tertiary cathode material and preparation method thereof,
Process conditions are simple, are easily achieved, easy to operate, improve the primary particle conjugation of nickelic tertiary cathode material, keep it primary
Particle combines more preferably, and chemical property improves obvious.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of nickelic tertiary cathode material, includes the following steps,
Step 1, by nickelic ternary metal salt and nano-cellulose fiber, ultrasonic disperse is uniformly stood afterwards in deionized water,
Obtain mixed system A；
Wherein, the sum of concentration of ternary metal ion is 0.2~1.0mol/L, the cross sectional dimensions of nano-cellulose fiber
It is 1~1000 for 5~50nm, draw ratio, the mass ratio of nano-cellulose fiber and metal ion is 1:(10~36)；
Step 2, by mixed system A in conjunction with precipitating reagent, nickelic tertiary cathode material is prepared with hydro-thermal method or coprecipitation
Presoma；
Step 3, the presoma of nickelic tertiary cathode material is uniformly mixed with lithium source, 600~900 DEG C under oxygen atmosphere
Calcining 8~for 24 hours, obtain nickelic tertiary cathode material；
Wherein, lithium source is lithium carbonate or lithium hydroxide, mole of lithium in the precursor A and lithium source of nickelic tertiary cathode material
Than for 1:(1~1.1), heating rate is 2~8 DEG C/min.
Preferably, hydro-thermal method described in step 2 prepares the presoma of nickelic tertiary cathode material, includes the following steps,
Precipitating reagent is added in mixed system A in step 2a, is cooled to room temperature after reacting 3~15h at 100~220 DEG C,
Wherein precipitating reagent is urea or ammonium hydrogen carbonate；
Step 2b, reaction product washing, filtering and the drying that step 2a is obtained, before obtaining nickelic tertiary cathode material
Drive body.
Further, the molar ratio of urea or ammonium hydrogen carbonate and ternary metal ion summation is (1~5) in step 2a: 1.
Further, temperature is risen to by reaction temperature with the heating rate of 2~10 DEG C/min in step 2a.
Preferably, coprecipitation described in step 2 prepares the presoma of nickelic tertiary cathode material, including following step
Suddenly,
Step 2a, mixed system A and precipitating reagent are instilled in the ammonium hydroxide that concentration is 0.4~3.0mol/L react 3~for 24 hours,
It is aged and is cooled to room temperature later, wherein precipitating reagent is sodium hydroxide or sodium carbonate；
Step 2b, reaction product washing, filtering and the drying that step 2a is obtained, before obtaining nickelic tertiary cathode material
Drive body.
Further, the pH of sodium hydroxide solution is 10~12.5 in step 2a, the concentration of sodium carbonate liquor is 0.125~
0.5mol/L。
Further, mixed system A and precipitating reagent are in ammonium hydroxide in step 2a, under the mixing speed of 300~1500r/min
It is reacted with 55~80 DEG C.
Further, mixed system A and precipitating reagent are under the atmosphere of nitrogen or argon gas in step 2, with the speed of 1~3mL/min
Rate instills in ammonium hydroxide.
Preferably, the time of repose in step 1 be 1~for 24 hours.
A kind of nickelic tertiary cathode that the preparation method of tertiary cathode material nickelic as described in above-mentioned any one obtains
Material.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention prepares the preparation method of nickelic tertiary cathode material, is 5~50nm using cross sectional dimensions, draw ratio is
The template action of 1~1000 nano-cellulose fiber, by the characteristic of its large specific surface area and strong adsorption standing item
Nickel ion, cobalt ions, manganese ion can be sufficiently adsorbed under part, and when the sum of concentration of ternary metal ion is less than 0.2mol/L
The nickelic tertiary cathode material chemical property obtained later is bad, and it is easy to reunite to influence it that the sum of concentration is greater than 1.0mol/L
The chemical property of the nickelic tertiary cathode material obtained afterwards；By mixed system A in conjunction with precipitating reagent after use hydro-thermal method or coprecipitated
Shallow lake method prepares the presoma of nickelic tertiary cathode material；The presoma is uniformly mixed with lithium source, calcining can under oxygen atmosphere
So that nano-cellulose fiber is carbonized simultaneously and oxidation, and then remove, leaves poroid particle, i.e., nickelic tertiary cathode material；
The present invention is adjusted the nano-cellulose fiber content that feeds intake by the additional amount of the regulation total ion of metal, can get one
Secondary particle buildup is obvious, the preferably secondary nickelic ternary material particle of conjugation.
Further, the mixed system A of precipitating reagent is added, temperature is risen to by reaction temperature with the heating rate of 2~10 DEG C/min
Degree is not only avoided that the volatilization of lithium source increases, moreover it is possible to the reunion of second particle in the presoma of nickelic tertiary cathode material is avoided,
Uniformly compound presoma can be obtained.
Further, mixed system A and precipitating reagent be in ammonia spirit, is reacted with 55~80 DEG C, by while heating, while stir
It mixes, is cooled to room temperature after ageing, wash, filter and dry, can finally obtain uniformly compound presoma.
Further, mixed system A and precipitating reagent are instilled under the atmosphere of nitrogen or argon gas with the rate of 1~3mL/min
In ammonium hydroxide, it is not only avoided that the oxidation of manganese ion, moreover it is possible to avoid the group of second particle in the presoma of nickelic tertiary cathode material
It is poly-, uniformly compound presoma can be obtained.
Nickelic tertiary cathode material of the invention and Nanowire is not added by the electrochemical property test of lithium ion battery
The nickelic tertiary cathode material of cellulose fiber is compared, and electrochemical impedance is substantially reduced, and cycle performance is obviously improved, being capable of certain journey
Degree ground improves the specific capacity of lithium ion battery, has preferable stability in constant temperature charge-discharge test；In addition, the material does not have
Extra substance generates, and will not cause damages to environment.
Detailed description of the invention
Fig. 1 is the nickelic tertiary cathode material forerunner that nano-cellulose fiber is not added of hydro-thermal method synthesis in comparative example 1
The scanning electron microscope (SEM) photograph of body.
Fig. 2 is the scanning electron microscope (SEM) photograph of the nickelic ternary anode material precursor of hydro-thermal method synthesis in embodiment 1.
Fig. 3 is sweeping for the nickelic tertiary cathode material that nano-cellulose fiber is not added that hydro-thermal method synthesizes in comparative example 1
Retouch electron microscope.
Fig. 4 is the scanning electron microscope (SEM) photograph of the nickelic tertiary cathode material of hydro-thermal method synthesis in embodiment 1.
Fig. 5 does not add for what the nickelic tertiary cathode material of hydro-thermal method synthesis in embodiment 1 was synthesized with hydro-thermal method in comparative example 1
Enter cyclic curve figure of the nickelic tertiary cathode material of nano-cellulose fiber under the conditions of 0.5C.
Fig. 6 is that the nickelic tertiary cathode material of Co deposited synthesis in embodiment 1 synthesizes not with hydro-thermal method in comparative example 2
Cyclic curve figure of the nickelic tertiary cathode material of nano-cellulose fiber under the conditions of 0.5C is added.
Fig. 7 does not add for what the nickelic tertiary cathode material of hydro-thermal method synthesis in embodiment 1 was synthesized with hydro-thermal method in comparative example 1
Enter the electrochemical impedance effect picture of the nickelic tertiary cathode material of nano-cellulose fiber.
Fig. 8 is that the nickelic tertiary cathode material of Co deposited synthesis in embodiment 1 synthesizes not with hydro-thermal method in comparative example 2
The electrochemical impedance effect picture of the nickelic tertiary cathode material of nano-cellulose fiber is added.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The present invention is using nano-cellulose fiber as auxiliary material, different from method of modifying such as existing cladding, ion dopings, using water
Thermal method and coprecipitation prepare nickelic tertiary cathode material, by improving the conjugation of nickelic tertiary cathode material primary particle,
Lower the degrees of exposure of nickelic tertiary cathode material particle surface and electrolyte, specifically include following two technical solution:
Scheme 1, hydro-thermal method synthesis, specifically includes following steps,
Step 1, corresponding nickel salt, cobalt salt and manganese salt are weighed according to the molar ratio of nickel, cobalt and manganese in ternary metal salt, with
And nano-cellulose fiber, it is equal that nickel salt, cobalt salt and manganese salt and nano-cellulose fiber are mixed in ultrasonic disperse in deionized water
Even standing 1 afterwards~for 24 hours, it allows nano-cellulose fiber to give full play to suction-operated, obtains mixed system A；
Wherein, the sum of concentration of metal ion in solution be 0.2~1.0mol/L, when concentration be less than 0.2mol/L when after
Obtained nickelic tertiary cathode material chemical property is bad, and it is easy to reunite thus what influence obtained later that concentration is greater than 1.0mol/L
The chemical property of nickelic tertiary cathode material；Nano-cellulose fiber be cross sectional dimensions be 5~50nm, draw ratio be 1~
1000 rhabdolith can sufficiently adsorb ternary metal ion by the characteristic of its large specific surface area and strong adsorption in this way,
Obtain poroid material later, the mass ratio of nano-cellulose fiber and metal ion is 1:(10~36)；
Step 2, a certain amount of precipitating reagent is added in mixed system A to stir evenly, then with the heating of 2~10 DEG C/min
Rate increases temperature to 100~220 DEG C, to provide hydrothermal temperature, is cooled to after reacting 3~15h in a high pressure reaction kettle
Room temperature obtains the composite precursor of nickelic tertiary cathode material successively by washing, filtering and drying；
Wherein, precipitating reagent is urea or ammonium hydrogen carbonate, in urea or ammonium hydrogen carbonate and solution nickel ion, cobalt ions and manganese from
The molar ratio of sub- summation is (1~5): 1, heating rate be 2~10 DEG C/min can make mixture sintering, when lower than 2 DEG C/
The efficiency in experimentation can be reduced when min, when be higher than 10 DEG C/min when can accelerate the reunion of primary particle and be unfavorable for into
The formation of single step reaction；
Step 3, by the presoma of nickelic tertiary cathode material with as lithium source lithium carbonate or lithium hydroxide by centainly matching
Than after mixing, the case where being passed through oxygen with the flow of 0.2~1L/min, high-temperature calcination 8 being carried out at 600~900 DEG C
~for 24 hours, so that nano-cellulose fiber is carbonized simultaneously and oxidation, and then remove, obtains nickelic tertiary cathode material A；
Wherein the molar ratio of the presoma of nickelic tertiary cathode material and lithium hydroxide is 1:(1~1.1), with lithium carbonate
Molar ratio is 1:(0.5~0.55), presoma and lithium hydroxide ground and mixed are in dehydrated alcohol, after volatile dry, under vacuum
It is dry, it is ground to uniformly mixed, heating rate is 2~8 DEG C/min, can make reaction more complete in this way, when being lower than 2 DEG C/min
When will increase the volatilization of lithium source, the reunion of second particle can be accelerated when being higher than 8 DEG C/min.
Scheme 2, coprecipitation specifically include following steps,
Step 1, corresponding nickel salt, cobalt salt and manganese salt are weighed according to the molar ratio of nickel, cobalt and manganese in ternary metal salt, with
And that nickel salt, cobalt salt and manganese salt and nano-cellulose fiber be mixed in ultrasonic disperse in deionized water is uniform for nano-cellulose fiber
Afterwards stand 1~for 24 hours, allow nano-cellulose fiber to give full play to suction-operated, obtain mixed system B；
Wherein, the sum of concentration of metal ion in solution be 0.2~1.0mol/L, when concentration be less than 0.2mol/L when after
Obtained nickelic tertiary cathode material chemical property is bad, and it is easy to reunite thus what influence obtained later that concentration is greater than 1.0mol/L
The chemical property of nickelic tertiary cathode material；Nano-cellulose fiber be cross sectional dimensions be 5~50nm, draw ratio be 1~
1000 rhabdolith can sufficiently adsorb ternary metal ion by the characteristic of its large specific surface area and strong adsorption in this way,
Obtain poroid material later, the mass ratio of nano-cellulose fiber and metal ion is 1:(10~36)；
Step 2, respectively by mixed system B and precipitating reagent under the atmosphere of nitrogen or argon gas, with the speed of 1~3mL/min
Rate instills in the enveloping agent solution of appropriate concentration simultaneously, and heating temperature is 55~80 DEG C, with the stirring speed of 300~1500r/min
Degree carries out reaction 3~for 24 hours while stirring, is cooled to room temperature after being aged later, successively by washing, filtering and dry, obtains height
The presoma of nickel tertiary cathode material；
Wherein, precipitating reagent is sodium hydroxide or sodium carbonate, and complexing agent is ammonium hydroxide, the pH of sodium hydroxide solution is 10~
12.5, the concentration of sodium carbonate liquor is 0.125~0.5mol/L, and the concentration of ammonium hydroxide is 0.4~3.0mol/L, wherein drop rate
Manganese ion can aoxidize when lower than 1mL/min, can reunite when higher than 3mL/min；
Step 3, by the presoma of nickelic tertiary cathode material with as lithium source lithium carbonate or lithium hydroxide be uniformly mixed
Afterwards, the case where being passed through oxygen with the flow of 0.2~1L/min, high-temperature calcination 8~for 24 hours is carried out at 600~900 DEG C, so that
Nano-cellulose fiber is carbonized simultaneously and oxidation, and then removes, and obtains nickelic tertiary cathode material B；
Wherein the molar ratio of the presoma of nickelic tertiary cathode material and lithium hydroxide is 1:(1~1.1), with lithium carbonate
Molar ratio is 1:(0.5~0.55), presoma and lithium hydroxide ground and mixed are in dehydrated alcohol, after volatile dry, under vacuum
It is dry, it is ground to uniformly mixed, heating rate is 2~8 DEG C/min, can make mixture sintering in this way, when being lower than 2 DEG C/min
The volatilization that will increase lithium source can accelerate the reunion of second particle when being higher than 8 DEG C/min.
Solvent in above two synthetic method may be dehydrated alcohol or ethanol solution, the body of ethyl alcohol in ethanol solution
Product accounting can not have to limit.
Embodiment 1
A kind of preparation method of nickelic tertiary cathode material of the present invention, includes the following steps,
Scheme 1, hydrothermal synthesis method,
Step 1a weighs the ternary nitrate that total ion concentration is the nickel of 0.2mol/L, cobalt and manganese, i.e. nickel nitrate, nitric acid
Cobalt and manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, then weigh the mass ratio with metal ion
For the nano-cellulose fiber of 1:16, be add to deionized water together, ultrasonic disperse uniformly and stand 1h, then be added with from
Sub- solution concentration molar ratio is the urea of 1:1, pours into autoclave after mixing evenly, heating rate is 5 DEG C/min, 120
6h is reacted at DEG C, is cooled to room temperature, and successively washing, filtering and drying, obtain the composite precursor of nickelic tertiary cathode material；
Step 1b is that 1:1.05 weighs hydrogen-oxygen according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium hydroxide
Change lithium, ultrasonic mixing is in dehydrated alcohol after then grinding, and after volatile dry, lower 110 DEG C of vacuum dry 12h are to prevent mixture
Oxidation, grinds later, and the case where being passed through oxygen with the flow of 0.2L/min, heating rate is 5 DEG C/min, in 650 DEG C of high temperature
12h is calcined, nickelic tertiary cathode material is obtained.
Comparative example 1
Step 1, the ternary nitrate that total ion concentration is the nickel of 0.2mol/L, cobalt and manganese, i.e. nickel nitrate, cobalt nitrate are weighed
And manganese nitrate, nickel, cobalt, manganese are weighed with molar ratio 80%, 10%, 10% respectively, are add to deionized water, ultrasonic disperse is uniform
And 1h is stood, the urea for being 1:1 with solion concentration molar ratio is then added, pours into autoclave after mixing evenly, rises
Warm rate is 5 DEG C/min, reacts 6h at 120 DEG C, is cooled to room temperature, and successively washing, filtering and drying, obtain precursor A；
It step 2, is that 1:1.05 weighs hydrogen-oxygen according to the molar ratio of the presoma of nickelic tertiary cathode material and lithium hydroxide
Change lithium, ultrasonic mixing is in dehydrated alcohol after then grinding, and after volatile dry, lower 110 DEG C of vacuum dry 12h are to prevent mixture
Oxidation, grinds later, and the case where being passed through oxygen with the flow of 0.2L/min, heating rate is 5 DEG C/min, in 650 DEG C of high temperature
12h is calcined, the nickelic tertiary cathode material of nano-cellulose fiber is not added.
Hydro-thermal method synthesis nickelic ternary anode material precursor scanning electron microscope (SEM) photograph and nano-cellulose fiber is not added
Nickelic ternary anode material precursor scanning electron microscope (SEM) photograph it is as depicted in figs. 1 and 2, it can be seen that Templated persursor material
Has the characteristics that more uniform, smaller primary particle partial size.
BET test is carried out by the nickelic tertiary cathode material obtained to embodiment 1 and comparative example 1, embodiment 1 can be obtained
Nickelic tertiary cathode material average grain diameter be 79nm, the nickelic tertiary cathode material average grain diameter of comparative example 1 is 178nm, because
This can illustrate that Templated material has the characteristics that smaller primary particle partial size, and not due to the presoma ratio of the material
The presoma that nano-cellulose fiber is added is more uniform, so finally obtained material is not also necessarily than nano-cellulose is added
The material of fiber is more uniform.
Hydro-thermal method synthesis nickelic tertiary cathode material scanning electron microscope (SEM) photograph and the nickelic of nano-cellulose fiber is not added
The scanning electron microscope (SEM) photograph of tertiary cathode material, as shown in Fig. 4 and Fig. 3, by comparison it can be found that the one of nickelic tertiary cathode material
Secondary particle buildup is obvious, and conjugation is more preferable, in conjunction with closer.Fig. 5 is nickelic tertiary cathode material and the comparison of hydro-thermal method synthesis
Circulation of the nickelic tertiary cathode material that nano-cellulose fiber is not added that hydro-thermal method synthesizes in example 1 under the conditions of 0.5C multiplying power
Performance, wherein 1C=280mA.h/g, it can be found that nickelic tertiary cathode material improves the specific capacity of lithium ion battery, in perseverance
There is preferable stability in warm charge-discharge test.
Fig. 7 does not add for what the nickelic tertiary cathode material of hydro-thermal method synthesis in embodiment 1 was synthesized with hydro-thermal method in comparative example 1
Enter the electrochemical impedance effect picture of the nickelic tertiary cathode material of nano-cellulose fiber, wherein ohm is ohm, and ordinate is resistance
It is anti-.Can be seen that addition nano-cellulose fiber from impedance analysis figure can be substantially reduced the impedance in charge and discharge process, from
And chemical property improves.
Scheme 2, coprecipitation method,
Step 2a weighs the ternary nitrate that total ion concentration is the nickel of 0.2mol/L, cobalt and manganese, i.e. nickel nitrate, nitric acid
Cobalt and manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, then weigh the mass ratio with metal ion
For the nano-cellulose fiber of 1:16, it is added to deionized water together, stands 1h, ultrasonic disperse is uniform, is with ammonia concn
0.4mol/L is standard, ammonium hydroxide is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water, then in the atmosphere of nitrogen
The lower hydrogen that using dropping funel while into four-hole boiling flask, rate addition ternary metal salting liquid and pH with 2mL/min are 11
Sodium hydroxide solution has an impact reaction to prevent external environment, and 55 DEG C of magnetic agitation are heated and in the mixing speed of 650r/min
Lower reaction 6h is cooled to room temperature after being aged later, and successively washing, filtering and drying, obtain the forerunner of nickelic tertiary cathode material
Body；
Step 2b is that 1:1.05 weighs hydrogen-oxygen according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium hydroxide
Change lithium, ultrasonic mixing is in dehydrated alcohol after then grinding, and after volatile dry, lower 110 DEG C of vacuum dry 12h are to prevent mixture
Oxidation, grinds later, and the case where being passed through oxygen with the flow of 0.2L/min, heating rate is 5 DEG C/min, in 600 DEG C of high temperature
12h is calcined, nickelic tertiary cathode material is obtained.
Comparative example 2
Step 1, the ternary nitrate that total ion concentration is the nickel of 0.2mol/L, cobalt and manganese, i.e. nickel nitrate, cobalt nitrate are weighed
And manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, are added to deionized water, stand 1h, ultrasound point
It dissipates uniformly, is 0.4mol/L as standard using ammonia concn, ammonia is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water
Ternary metal is added then using dropping funel while into four-hole boiling flask under the atmosphere of nitrogen with the rate of 2mL/min in water
The sodium hydroxide solution that salting liquid and pH are 11, has an impact reaction to prevent external environment, 55 DEG C of magnetic agitation heating and
6h is reacted under the mixing speed of 650r/min, is cooled to room temperature after being aged later, and successively washing, filtering and drying, obtain forerunner
Body B；
It step 2, is that 1:1.05 weighs hydrogen-oxygen according to the molar ratio of the presoma of nickelic tertiary cathode material and lithium hydroxide
Change lithium, ultrasonic mixing is in dehydrated alcohol after then grinding, and after volatile dry, lower 110 DEG C of vacuum dry 12h are to prevent mixture
Oxidation, grinds later, and the case where being passed through oxygen with the flow of 0.2L/min, heating rate is 5 DEG C/min, in 600 DEG C of high temperature
12h is calcined, the nickelic tertiary cathode material of nano-cellulose fiber is not added.
BET test is carried out by the nickelic tertiary cathode material obtained to embodiment 1 and comparative example 2, embodiment 1 can be obtained
Nickelic tertiary cathode material average grain diameter is 96nm, and the nickelic tertiary cathode material average grain diameter of comparative example 2 is 190nm, therefore
It can illustrate that Templated material has the characteristics that smaller primary particle partial size, and since the presoma of the material is not than adding
The presoma for entering nano-cellulose fiber is more uniform, so finally obtained material is not also necessarily than nano-cellulose fibre is added
The material of dimension is more uniform.
Nickelic three that nano-cellulose fiber is not added that the nickelic tertiary cathode material is synthesized with hydro-thermal method in comparative example 2
Cycle performance of first positive electrode under the conditions of 0.5C multiplying power, as shown in fig. 6, wherein 1C=280mA.h/g, it can be found that nickelic
Tertiary cathode material improves the specific capacity of lithium ion battery, has preferable stability in constant temperature charge-discharge test, in turn
It can illustrate that the primary particles aggregate of the nickelic tertiary cathode material is obvious, conjugation is more preferable, in conjunction with closer.
Fig. 8 is that the nickelic tertiary cathode material of Co deposited synthesis in embodiment 1 synthesizes not with hydro-thermal method in comparative example 2
The electrochemical impedance effect picture of the nickelic tertiary cathode material of nano-cellulose fiber is added, wherein ohm is ohm, and ordinate is
Impedance.Can be seen that addition nano-cellulose fiber from impedance analysis figure can be substantially reduced the impedance in charge and discharge process,
To which chemical property improves.
Embodiment 2
A kind of preparation method of nickelic tertiary cathode material of the present invention, includes the following steps,
Scheme 1, hydrothermal synthesis method,
Step 1a, weighs the ternary nitrate that total solion concentration is the nickel of 0.4mol/L, cobalt and manganese, i.e., nickel nitrate,
Cobalt nitrate and manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, then weigh the matter with metal ion
Amount is added in dehydrated alcohol together than the nano-cellulose fiber for being 1:20, stands 5h, ultrasonic disperse is uniform, is then added
The ammonium hydrogen carbonate for being 2:1 with solion concentration molar ratio, pours into autoclave after mixing evenly, and heating rate is 2 DEG C/
Min reacts 3h at 140 DEG C, is cooled to room temperature, and successively washs, filters, is dry, obtaining the compound of nickelic tertiary cathode material
Presoma；
Step 1b is that 1:0.5 weighs carbonic acid according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium hydroxide
Lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 0.4L/min is passed through oxygen, heating rate obtain nickelic three in 700 DEG C of high-temperature calcination 15h for 2 DEG C/min
First positive electrode.
Scheme 2, coprecipitation method,
Step 2a weighs the ternary nitrate that total ion concentration is the nickel of 0.4mol/L, cobalt and manganese, i.e. nickel nitrate, nitric acid
Cobalt and manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, then weigh the mass ratio with metal ion
For the nano-cellulose fiber of 1:20, it is added to deionized water together, stands 5h, ultrasonic disperse is uniform, is with ammonia concn
1mol/L is standard, and ammonium hydroxide is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water, then makes under an argon atmosphere
With dropping funel while into four-hole boiling flask, the hydrogen-oxygen that ternary metal salting liquid and pH are 12.5 is added with the rate of 3mL/min
Change sodium solution, 60 DEG C of magnetic agitation are heated and reacted for 24 hours under the mixing speed of 300r/min, are cooled to room after being aged later
Temperature successively washs, filters, is dry, obtaining the presoma of nickelic tertiary cathode material；
Step 2b is that 1:1.1 weighs hydrogen-oxygen according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium hydroxide
Change lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 0.4L/min is passed through oxygen, heating rate are 2 DEG C/min, and 650 DEG C of high-temperature calcination 15h obtain nickelic ternary
Positive electrode.
Embodiment 3
A kind of preparation method of nickelic tertiary cathode material of the present invention, includes the following steps,
Scheme 1, hydrothermal synthesis method,
Step 1a weighs the ternary nitrate of nickel, cobalt, manganese that total ion concentration is 0.6mol/L, i.e. nickel nitrate, cobalt nitrate
And manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, are then weighed and are with the mass ratio of metal ion
The nano-cellulose fiber of 1:24, is add to deionized water together, stands 10h, and ultrasonic disperse is uniform, then addition and ion
Solution concentration molar ratio is the urea of 2.5:1, pours into autoclave after mixing evenly, heating rate is 10 DEG C/min, 160
10h is reacted at DEG C, is cooled to room temperature, and is successively washed, is filtered, is dry, obtaining the presoma of nickelic tertiary cathode material；
Step 1b is that 1:1 weighs hydroxide according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium hydroxide
Lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 0.6L/min is passed through oxygen, heating rate obtain nickelic three in 600 DEG C of high-temperature calcination 18h for 8 DEG C/min
First positive electrode.
Scheme 2, coprecipitation method,
Step 2a weighs the ternary nitrate that total ion concentration is the nickel of 0.6mol/L, cobalt and manganese, i.e. nickel nitrate, nitric acid
Cobalt and manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, then weigh the mass ratio with metal ion
For the nano-cellulose fiber of 1:24, it is added to deionized water together, stands 10h, ultrasonic disperse is uniform, is with ammonia concn
1.5mol/L is standard, ammonium hydroxide is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water, then in a nitrogen atmosphere
Using dropping funel while into four-hole boiling flask, the hydroxide that ternary metal salting liquid and pH are 0 is added with the rate of 1mL/min
Sodium solution, 65 DEG C of magnetic agitation are heated and react 10h under the mixing speed of 750r/min, are cooled to room temperature after being aged later,
It successively washs, filter, is dry, obtaining the presoma of nickelic tertiary cathode material；
Step 2b is that 1:0.5 weighs lithium carbonate according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium carbonate,
Then ultrasonic mixing is in dehydrated alcohol after grinding, and after volatile dry, 110 DEG C of vacuum dry 12h are ground, later with 0.6L/
The case where flow of min is passed through oxygen, heating rate are 8 DEG C/min, and 700 DEG C of high-temperature calcination 18h obtain nickelic tertiary cathode material
Material.
Embodiment 4
A kind of preparation method of nickelic tertiary cathode material of the present invention, includes the following steps,
Scheme 1, hydrothermal synthesis method,
Step 1a, weighs the ternary nitrate that total ion concentration is the nickel of 1mol/L, cobalt, manganese, i.e., nickel nitrate, cobalt nitrate and
Manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, and then weighing with the mass ratio of metal ion is 1:
28 nano-cellulose fiber, being added to volume ratio together is to stand 15h in 50% ethanol solution, and ultrasonic disperse is uniform,
Then the urea for being 3:1 with solion concentration molar ratio is added, pours into autoclave, heating rate 3 after mixing evenly
DEG C/min, 12h is reacted at 180 DEG C, is cooled to room temperature, successively washs, filter, is dry, obtaining nickelic tertiary cathode material
Composite precursor；
Step 1b is that 1:0.53 weighs hydroxide according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium carbonate
Lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 0.6L/min is passed through oxygen, heating rate obtain nickelic three in 780 DEG C of high-temperature calcination 20h for 3 DEG C/min
First positive electrode.
Scheme 2, coprecipitation method,
Step 2a, weighs the ternary nitrate that total ion concentration is the nickel of 1mol/L, cobalt, manganese, i.e., nickel nitrate, cobalt nitrate and
Manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, and then weighing with the mass ratio of metal ion is 1:
10 nano-cellulose fiber is added to deionized water together, stands 15h, ultrasonic disperse is uniform, is 2mol/L with ammonia concn
For standard, ammonium hydroxide is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water, then uses dropping liquid under an argon atmosphere
Into four-hole boiling flask, the carbonic acid of ternary metal salting liquid and 0.125~0.5mol/L is added with the rate of 3mL/min simultaneously for funnel
Sodium solution, 70 DEG C of magnetic agitation are heated and react 12h under the mixing speed of 1000r/min, are cooled to room temperature after being aged later,
It successively washs, filter, is dry, obtaining the presoma of nickelic tertiary cathode material；
Step 2b is that 1:0.51 weighs hydroxide according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium carbonate
Lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 0.6L/min is passed through oxygen, heating rate are 6 DEG C/min, and 800 DEG C of high-temperature calcination 20h obtain nickelic ternary
Positive electrode.
Embodiment 5
A kind of preparation method of nickelic tertiary cathode material of the present invention, includes the following steps,
Scheme 1, hydrothermal synthesis method,
Step 1a weighs the ternary nitrate of nickel, cobalt, manganese that total ion concentration is 0.8mol/L, i.e. nickel nitrate, cobalt nitrate
And manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, are then weighed and are with the mass ratio of metal ion
The nano-cellulose fiber of 1:10, is added in dehydrated alcohol together, stands 20h, and ultrasonic disperse is uniform, then addition and ion
Solution concentration molar ratio is 4:
1 ammonium hydrogen carbonate pours into autoclave after mixing evenly, and heating rate is 8 DEG C/min, reacts at 100 DEG C
15h is cooled to room temperature, and is successively washed, is filtered, is dry, obtaining the composite precursor of nickelic tertiary cathode material；
Step 1b is that 1:1.1 weighs hydrogen-oxygen according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium hydroxide
Change lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 1L/min is passed through oxygen, heating rate be 6 DEG C/min, 800 DEG C of high-temperature calcinations for 24 hours, obtain nickelic ternary
Positive electrode.
Scheme 2, coprecipitation method,
Step 2a weighs the ternary nitrate of nickel, cobalt, manganese that total ion concentration is 0.8mol/L, i.e. nickel nitrate, cobalt nitrate
And manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, are then weighed and are with the mass ratio of metal ion
The nano-cellulose fiber of 1:32 is added to deionized water together, stands 20h, ultrasonic disperse is uniform, is with ammonia concn
2.5mol/L is standard, ammonium hydroxide is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water, then in a nitrogen atmosphere
Using dropping funel while into four-hole boiling flask, the carbon of ternary metal salting liquid and 0.5mol/L is added with the rate of 1mL/min
Acid sodium solution, 75 DEG C of magnetic agitation are heated and react 15h under the mixing speed of 1500r/min, are cooled to room after being aged later
Temperature successively washs, filters, is dry, obtaining the presoma of nickelic tertiary cathode material；
Step 2b is that 1:0.55 weighs carbonic acid according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium carbonate
Lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 1L/min is passed through oxygen, heating rate are 7 DEG C/min, and 850 DEG C of high-temperature calcinations for 24 hours, are obtaining nickelic ternary just
Pole material.
Embodiment 6
A kind of preparation method of nickelic tertiary cathode material of the present invention, includes the following steps,
Scheme 1, hydrothermal synthesis method,
Step 1a weighs the ternary nitrate of nickel, cobalt, manganese that total ion concentration is 0.5mol/L, i.e. nickel nitrate, cobalt nitrate
And manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, are then weighed and are with the mass ratio of metal ion
The nano-cellulose fiber of 1:36, is add to deionized water together, stands for 24 hours, and ultrasonic disperse is uniform, then addition and ion
Solution concentration molar ratio is the urea of 5:1, pours into autoclave after mixing evenly, heating rate is 6 DEG C/min, at 220 DEG C
Lower reaction 8h, is cooled to room temperature, and successively washs, filters, is dry, obtaining the composite precursor of nickelic tertiary cathode material；
Step 1b is that 1:0.55 weighs hydroxide according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium carbonate
Lithium, then grind after ultrasonic mixing in dehydrated alcohol, after volatile dry, 110 DEG C of vacuum dry 12h are ground later, with
The case where flow of 0.5L/min is passed through oxygen, heating rate obtain nickelic ternary in 900 DEG C of high-temperature calcination 8h for 4 DEG C/min
Positive electrode.
Scheme 2, coprecipitation method,
Step 2a weighs nickel, cobalt that total ion concentration is 0.5mol/L, the ternary nitrate of manganese ternary, i.e. nickel nitrate, nitre
Sour cobalt and manganese nitrate, nickel, cobalt, manganese are weighed respectively with molar ratio 80%, 10%, 10%, then weigh the quality with metal ion
Than the nano-cellulose fiber for 1:36, it is added to deionized water together, stands for 24 hours, ultrasonic disperse is uniform, is with ammonia concn
3mol/L is standard, and ammonium hydroxide is added in the four-hole boiling flask of the bottom liquid containing 200mL deionized water, then makes under an argon atmosphere
With dropping funel while into four-hole boiling flask, the carbonic acid of ternary metal salting liquid and 0.25mol/L is added with the rate of 2mL/min
Sodium solution, 80 DEG C of magnetic agitation are heated and react 3h under the mixing speed of 900r/min, are cooled to room temperature after being aged later, according to
Secondary washing, filtering, drying, obtain the composite precursor of nickelic tertiary cathode material；
Step 2b is that 1:1 weighs lithium hydroxide according to the presoma of nickelic tertiary cathode material and the molar ratio of lithium carbonate,
Then ultrasonic mixing is in dehydrated alcohol after grinding, and after volatile dry, 110 DEG C of vacuum dry 12h are ground, later with 0.5L/
The case where flow of min is passed through oxygen, heating rate are 8 DEG C/min, and 900 DEG C of high-temperature calcination 8h obtain nickelic tertiary cathode material
Material.
Above disclosure simultaneously describes basic principle and technical characteristics and advantages of the present invention of the invention.This field
Technical staff it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment simply to illustrate that
The principle of the present invention, under the premise of not departing from present inventive concept and concept, various changes and improvements may be made to the invention,
These changes and improvements all should belong to the range of embodiment of the present invention.
Claims (10)
1. a kind of preparation method of nickelic tertiary cathode material, which is characterized in that include the following steps,
Step 1, by nickelic ternary metal salt and nano-cellulose fiber, ultrasonic disperse is uniformly stood afterwards in deionized water, is obtained
Mixed system A；
Wherein, the sum of concentration of ternary metal ion is 0.2~1.0mol/L, and the cross sectional dimensions of nano-cellulose fiber is 5
~50nm, draw ratio are 1~1000, and the mass ratio of nano-cellulose fiber and metal ion is 1:(10~36)；
Step 2, by mixed system A in conjunction with precipitating reagent, before preparing nickelic tertiary cathode material with hydro-thermal method or coprecipitation
Drive body；
Step 3, the presoma of nickelic tertiary cathode material is uniformly mixed with lithium source, 600~900 DEG C of calcinings under oxygen atmosphere
8~for 24 hours, obtain nickelic tertiary cathode material；
Wherein, lithium source is lithium carbonate or lithium hydroxide, and the molar ratio of lithium is in the precursor A and lithium source of nickelic tertiary cathode material
1:(1~1.1), heating rate is 2~8 DEG C/min.
2. a kind of preparation method of nickelic tertiary cathode material according to claim 1, which is characterized in that institute in step 2
The hydro-thermal method stated prepares the presoma of nickelic tertiary cathode material, includes the following steps,
Precipitating reagent is added in mixed system A in step 2a, is cooled to room temperature after reacting 3~15h at 100~220 DEG C, wherein
Precipitating reagent is urea or ammonium hydrogen carbonate；
Step 2b, reaction product washing, filtering and the drying that step 2a is obtained, obtains the forerunner of nickelic tertiary cathode material
Body.
3. a kind of preparation method of nickelic tertiary cathode material according to claim 2, which is characterized in that urinated in step 2a
The molar ratio of element or ammonium hydrogen carbonate and ternary metal ion summation is (1~5): 1.
4. a kind of preparation method of nickelic tertiary cathode material according to claim 2, which is characterized in that in step 2a with
Temperature is risen to reaction temperature by the heating rate of 2~10 DEG C/min.
5. a kind of preparation method of nickelic tertiary cathode material according to claim 1, which is characterized in that institute in step 2
The coprecipitation stated prepares the presoma of nickelic tertiary cathode material, includes the following steps,
Step 2a, mixed system A and precipitating reagent are instilled in the ammonium hydroxide that concentration is 0.4~3.0mol/L react 3~for 24 hours, later
It is aged and is cooled to room temperature, wherein precipitating reagent is sodium hydroxide or sodium carbonate；
Step 2b, reaction product washing, filtering and the drying that step 2a is obtained, obtains the forerunner of nickelic tertiary cathode material
Body.
6. a kind of preparation method of nickelic tertiary cathode material according to claim 5, which is characterized in that hydrogen in step 2a
The pH of sodium hydroxide solution is 10~12.5, and the concentration of sodium carbonate liquor is 0.125~0.5mol/L.
7. a kind of preparation method of nickelic tertiary cathode material according to claim 5, which is characterized in that mixed in step 2a
Zoarium system A and precipitating reagent are reacted in ammonium hydroxide under the mixing speed of 300~1500r/min with 55~80 DEG C.
8. a kind of preparation method of nickelic tertiary cathode material according to claim 5, which is characterized in that mixed in step 2
Zoarium system A and precipitating reagent are instilled in ammonium hydroxide under the atmosphere of nitrogen or argon gas with the rate of 1~3mL/min.
9. a kind of preparation method of nickelic tertiary cathode material according to claim 1, which is characterized in that in step 1
Time of repose be 1~for 24 hours.
10. a kind of preparation method of tertiary cathode material nickelic as described in any one of claim 1~9 obtains nickelic
Tertiary cathode material.
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