CN107799741A - A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide - Google Patents

A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide Download PDF

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CN107799741A
CN107799741A CN201710897989.4A CN201710897989A CN107799741A CN 107799741 A CN107799741 A CN 107799741A CN 201710897989 A CN201710897989 A CN 201710897989A CN 107799741 A CN107799741 A CN 107799741A
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cobalt
nickel
zinc oxide
ion battery
positive electrode
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袁高清
张晨
付海阔
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South China University of Technology SCUT
Guangdong Jiana Energy Technology Co Ltd
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South China University of Technology SCUT
Guangdong Jiana Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of preparation method of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide.Preparation method of the present invention is by after nickel-cobalt-manganese ternary precursor powder mixes with lithium carbonate made from coprecipitation, pass through roasting oxidation, again with zinc source power in ammoniacal liquor or ultra-pure water miscible formation suspension, finally suspension is evaporated, dried, again through calcining, the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide is obtained.The raw material sources of preparation method of the present invention are cheap and easy to get, synthesis technique is simple, temperature is low, sintering time is short, without strictly controlling the pH value of solution in course of reaction, it is easily achieved industrialization, in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of obtained modified zinc oxide, lithiumation proportioning is high, and zinc oxide is dispersed on nickel cobalt manganese lithium particle surface；Meanwhile the lithium ion battery nickel-cobalt-manganese ternary positive electrode of obtained modified zinc oxide has extended cycle life, good cycle, the charge-discharge performance of lithium ion battery can be effectively improved.

Description

A kind of preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide Method
Technical field
The present invention relates to field of lithium ion battery, and in particular to the preparation of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide Method.
Background technology
With becoming increasingly conspicuous the problems such as energy crisis and environmental pollution, the new energy of Sustainable Development, build low Carbon society turns into the task of top priority.Lithium ion battery receives much concern as a kind of novel high-energy green battery.Lithium ion battery is existing The major advantage of high voltage, high power capacity, there is the distinguishing feature for having extended cycle life, having a safety feature again.Set in portable electronic The many-side such as standby, electric automobile, space technology, national defense industry illustrates wide application prospect, rapidly becomes and closed in the last few years The study hotspot of note.
Nickel-cobalt-manganternary ternary anode material be there are problems that in actual production and application.In terms of material preparation, when Material sintering temperature easily causes oxygen missing when too high, produce some impurities phases, cause the specific capacity of material to decline, and circulates Performance can also reduce, especially under the conditions of big multiplying power discharging.In the application, when nickel content increase in nickel cobalt manganese lithium ternary material Afterwards, material is easy to and CO in atmosphere2And H2O, which reacts, generates Li2CO3And LiOH, and the LiOH and LiPF in electrolyte6 React and produce HF.Secondly under high voltage environment during discharge and recharge, Ni of the electrolyte by high oxidation state in positive electrode4+'s Induce and decompose, form boundary layer in positive electrode and electrolyte contacts face, boundary layer can reduce electric conductivity so as to increase The internal resistance of battery so that capacity is also further decayed.
Nickel cobalt can be significantly improved by optimizing sintering process, changing the means such as material morphology, bulk phase-doped, Surface coating The chemical property of manganese lithium anode material.Up to the present, some documents, patent report carry out ZnO to tertiary cathode material Coating modification.For example, Chinese patent（CN 105489856A）Report direct precipitation method and carry out ZnO coating modifications, using direct The problem of precipitation method, is Zn (OH)2Belong to amphoteric hydroxide, pH is difficult to control.Kong et al. uses Atomic layer deposition method （Journal of Power Sources, 2014, 226: 433-439）, in LiNi0.5Co0.2Mn0.3O2Sunk on positive electrode Ultra-thin ZnO coatings have been accumulated, have effectively improved the chemical property of the section bar material of nickel cobalt manganese 523.Guo et al. is with Zn (CH3COO)2· 2H2O is ZnO sources, using sol-gal process（（Electrochimica Acta, 2009,54：5796-5803）It is right LiNi0.5Co0.25Mn0.25O2Coated, achieve preferable covered effect.
But the shortcomings that technique is excessively complicated or cost is high be present in above-mentioned method of modifying, thus work out technique it is simple, Cost is low, and the modification method for preparing for being advantageous to improve nickel-cobalt-manganternary ternary anode material performance is significant.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of lithium ionic cell nickel of modified zinc oxide The preparation method of cobalt-manganese ternary positive electrode.The preparation method is by nickel-cobalt-manganese ternary precursor powder and carbon made from coprecipitation After the mixing of sour lithium, by roasting oxidation, then with zinc source power in ammoniacal liquor or ultra-pure water miscible formation suspension, will finally suspend Liquid is evaporated, dried, and obtained solid powder obtains the lithium ion battery nickel-cobalt-manganese ternary positive pole material of modified zinc oxide through calcining Material.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, comprises the following steps：
（1）Nickel sulfate, cobaltous sulfate and manganese sulfate is soluble in water, it is thoroughly mixed uniformly, obtains mixed solution；
（2）Sodium hydroxide solution and ammoniacal liquor are added to step（1）In obtained mixed solution, nickel cobalt is generated by coprecipitation Manganese ternary precursor powder；
（3）After nickel-cobalt-manganese ternary precursor powder is uniformly mixed with lithium carbonate powder, it is calcined, obtains in air or oxygen atmosphere To nickel cobalt manganese lithium oxide powder；
（4）Zinc source power is dissolved in excessive ammonia, obtains settled solution, adds nickel cobalt manganese lithium oxide powder, stirring is equal It is even, obtain suspension；
（5）By step（4）Obtained suspension slow evaporation is dried to being evaporated, and obtained solid powder is forged in air atmosphere Burn, obtain the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide.
Further, step（1）In, the mol ratio of the nickel sulfate, cobaltous sulfate and manganese sulfate is 4 ~ 6：1.7~2：2.5~ 3.5, preferably 5：2：3.
Further, step（1）In, the concentration of the mixed solution is 1.5 ~ 2.5mol/L, preferably 2mol/L.
Further, step（2）In, the concentration of the sodium hydroxide solution is 5 ~ 8mol/L, preferably 7mol/L.
Further, step（2）In, the concentration of the ammoniacal liquor is 4 ~ 7mol/L, preferably 6mol/L.
Further, step（2）In, during the coprecipitation reaction, control pH value of solution be 10.8 ± 0.1, ammonium root from Sub- concentration is 8.5 ± 0.2g/L, and temperature is 50 ~ 60 DEG C, reaction time 35h.
Further, step（2）In, the particle diameter D of the nickel-cobalt-manganese ternary precursor powder50For 10.5 ± 0.2 μm.
Further, step（2）In, the temperature of the coprecipitation reaction is preferably 55 DEG C.
Further, step（3）In, the lithiumation that the nickel-cobalt-manganese ternary precursor powder mixes with lithium carbonate powder matches For 1 ~ 1.3, i.e. M：Li=1:1 ~ 1.3, wherein M=Ni, Co and Mn.
Further, step（3）In, the temperature of the roasting is 750 ~ 900 DEG C, preferably 800 ~ 880 DEG C.
Further, step（3）In, the time of the roasting is 8 ~ 17 hours, preferably 12 hours.
Further, step（4）In, the zinc source includes zinc powder, zinc chloride, zinc sulfate or zinc gluconate.
It is further preferred that step（4）In, the zinc source is zinc gluconate, and ammoniacal liquor is substituted using ultra-pure water.
Further, step（4）In, the concentration of the ammoniacal liquor is 4 ~ 7mol/L, preferably 6mol/L.
Further, step（5）In, the drying is in 80 ~ 150 DEG C of drying in oven, preferably 100 DEG C.
Further, step（5）In, the temperature of the calcining is 400 ~ 800 DEG C, preferably 600 ~ 700 DEG C.
Further, step（5）In, the time of the calcining is 0.5 ~ 5 hour, preferably 2 ~ 5 hours, more preferably 3 Hour.
Further, in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide obtained, the matter of zinc oxide It is 0.3 ~ 5%, preferably 0.5% ~ 3% to measure fraction.
Compared with prior art, the invention has the advantages that and beneficial effect：
（1）The raw material sources of preparation method of the present invention are cheap and easy to get, and synthesis technique is simple, temperature is low, sintering time is short, without tight The pH value of solution in lattice control course of reaction, it is easy to accomplish industrialization；
（2）In the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide made from preparation method of the present invention, lithiumation is matched somebody with somebody Than high, and zinc oxide is dispersed on nickel cobalt manganese lithium particle surface；
（3）The cycle life of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide made from preparation method of the present invention Grow, good cycle, the charge-discharge performance of lithium ion battery can be effectively improved；In high pressure 4.6V, 1C constant current charge-discharge, lithium Change under the conditions of proportioning is 1.06, the capability retention that the nickel-cobalt-manganternary ternary anode material of not oxidised zinc modification circulates 50 times is only 80%, and the nickel-cobalt-manganternary ternary anode material of oxidized zinc modification circulates the capability retention of 50 times more than 94%；In high pressure 4.6V, 1C constant current charge-discharge, under the conditions of lithiumation proportioning is 1.15, the capability retention that circulation is 50 times is from unmodified 75.9% It is raised to modified more than 90%.
Brief description of the drawings
Fig. 1 is nickel cobalt manganese lithium oxide powder prepared by embodiment 1（Uncoated zinc oxide）SEM figure；
Fig. 2 a are the SEM figures of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 1；
Fig. 2 b are that CR2016 half-cells are permanent in 1C made of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 1 Flow 50 circulation figures of discharge and recharge；
Fig. 3 a are the SEM figures of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 2；
Fig. 3 b are that CR2016 half-cells are permanent in 1C made of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 2 Flow 50 circulation figures of discharge and recharge；
Fig. 4 a are the SEM figures of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 3；
Fig. 4 b are that CR2016 half-cells are permanent in 1C made of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 3 Flow 50 circulation figures of discharge and recharge；
Fig. 5 a are the SEM figures of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 4；
Fig. 5 b are that CR2016 half-cells are permanent in 1C made of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 4 Flow 50 circulation figures of discharge and recharge；
Fig. 6 a are the SEM figures of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 5；
Fig. 6 b are that CR2016 half-cells are permanent in 1C made of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 5 Flow 50 circulation figures of discharge and recharge；
Fig. 7 a are the SEM figures of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 6；
Fig. 7 b are that CR2016 half-cells are permanent in 1C made of the nickel-cobalt-manganternary ternary anode material of modified zinc oxide prepared by embodiment 6 Flow 50 circulation figures of discharge and recharge.
Embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and accompanying drawing, but application claims The scope of protection is not limited thereto.
Embodiment 1
The preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, specifically comprises the following steps：
（1）39.43kg NiSO are taken respectively4·6H2O、16.87kg CoSO4·7H2O and 15.21kg MnSO4·H2O, add water To 150L, stirring and dissolving, 150L concentration 2mol/L mixed solution is obtained；
（2）With peristaltic pump by concentration 7mol/L sodium hydroxide solution, concentration 6mol/L ammoniacal liquor and step（1）What is obtained is mixed Close solution to squeeze into reactor, the pH for keeping solution in reactor is 10.8, and ammonium ion concentration is 8.5, and temperature is 55 DEG C, is turned Speed is 280r/min, is shut down when reacting 35 hours by coprecipitation and reach 10.5 ± 0.2 μm to presoma particle diameter, dries, obtains To nickel-cobalt-manganese ternary precursor powder；
（3）By 20g nickel-cobalt-manganese ternaries precursor powder and 8.64g lithium carbonate powders（Lithiumation proportioning is 1.06）After well mixed, In resistance furnace, 800 DEG C are warming up to from room temperature with 5 DEG C/min of heating rate under air atmosphere, 11h is incubated in 800 DEG C；Insulation knot Cool to room temperature after beam with the furnace, obtain nickel cobalt manganese lithium oxide powder；
The SEM figures of obtained nickel cobalt manganese lithium oxide powder are as shown in figure 1, as shown in Figure 1, obtained cobalt nickel oxide manganses lithium powder Particle has become big, physically well develops, and without sintered bonds together, pattern is preferable.
（4）0.04g zinc powders are dissolved in 30ml ammoniacal liquor（AR）In, settled solution is obtained, then add into settled solution 10g nickel cobalt manganese lithium oxide powders, stir, obtain suspension；
（5）Heating stirring to suspension is evaporated, then is placed in 100 DEG C of baking ovens and is dried, and obtained solid powder is hollow in resistance furnace Under gas atmosphere, 600 DEG C are warming up to 5 DEG C/min of heating rate, in 600 DEG C of insulation calcining 3h, obtain the lithium of modified zinc oxide from Sub- battery nickel-cobalt-manganternary ternary anode material.
The SEM figures of the nickel-cobalt-manganternary ternary anode material of the modified zinc oxide of preparation are as shown in Figure 2 a, spherical from Fig. 2 a Uniformly cladding has gone up one layer of atrament to particle surface, compared to Figure 1 understands, particle surface has an obvious blackening, and pattern compared with It is good not change substantially before with uncoated.
CR2016 half-cells are made in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide of preparation, in electricity Press 4.6V, under the conditions of 1C constant current charge-discharges, 50 circulation figures of discharge and recharge as shown in Figure 2 b, from Fig. 2 b, 50 circulation volumes Conservation rate is by unmodified 79.2%（Specific discharge capacity drops to 153.1mAh/g by 188.9mAh/g）Rise to modified 94.95%（Specific discharge capacity drops to 169.1mAh/g by 178.1mAh/g）.
Embodiment 2
The preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, specifically comprises the following steps：
（1）39.43kg NiSO are taken respectively4·6H2O、16.87kg CoSO4·7H2O and 15.21kg MnSO4·H2O, add water To 150L, stirring and dissolving, 150L concentration 2mol/L mixed solution is obtained；
（2）With peristaltic pump by concentration 7mol/L sodium hydroxide solution, concentration 6mol/L ammoniacal liquor and step（1）What is obtained is mixed Close solution to squeeze into reactor, the pH for keeping solution in reactor is 10.8, and ammonium ion concentration is 8.5, and temperature is 55 DEG C, is turned Speed is 280r/min, is shut down when reacting 35 hours by coprecipitation and reach 10.5 ± 0.2 μm to presoma particle diameter, dries, obtains To nickel-cobalt-manganese ternary precursor powder；
（3）By 20g nickel-cobalt-manganese ternaries precursor powder and 9.14g lithium carbonate powders（Lithiumation proportioning is 1.12）After well mixed, In resistance furnace, 850 DEG C are warming up to from room temperature with 5 DEG C/min of heating rate under air atmosphere, 11h is incubated in 850 DEG C；Insulation knot Cool to room temperature after beam with the furnace, obtain nickel cobalt manganese lithium oxide powder；
Referring to Fig. 1, obtained cobalt nickel oxide manganses lithium powder particle has become the SEM figures of obtained nickel cobalt manganese lithium oxide powder Greatly, physically well develop, and without sintered bonds together, pattern is preferable.
（4）0.08g zinc powders are dissolved in 30ml ammoniacal liquor（AR）In, settled solution is obtained, then add into settled solution 10g nickel cobalt manganese lithium oxide powders, stir, obtain suspension；
（5）Heating stirring to suspension is evaporated, then is placed in 100 DEG C of baking ovens and is dried, and obtained solid powder is hollow in resistance furnace Under gas atmosphere, 650 DEG C are warming up to 5 DEG C/min of heating rate, in 650 DEG C of insulation calcining 3h, obtain the lithium of modified zinc oxide from Sub- battery nickel-cobalt-manganternary ternary anode material.
The SEM figures of the nickel-cobalt-manganternary ternary anode material of the modified zinc oxide of preparation are as shown in Figure 3 a, spherical from Fig. 3 a Uniformly cladding has gone up one layer of atrament to particle surface, is understood compared with cobalt nickel oxide manganses lithium powder particle, particle surface has Obvious blackening, and pattern does not change preferably substantially before with uncoated.
CR2016 half-cells are made in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide of preparation, in electricity Press 4.6V, under the conditions of 1C constant current charge-discharges, 50 circulation figures of discharge and recharge as shown in Figure 3 b, from Fig. 3 b, 50 circulation volumes Conservation rate is by unmodified 79.2%（Specific discharge capacity drops to 153.1mAh/g by 188.9mAh/g）Rise to modified 94.08%（Specific discharge capacity drops to 160.5mAh/g by 170.6mAh/g）.
Embodiment 3
The preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, specifically comprises the following steps：
（1）39.43kg NiSO are taken respectively4·6H2O、16.87kg CoSO4·7H2O and 15.21kg MnSO4·H2O, add water To 150L, stirring and dissolving, 150L concentration 2mol/L mixed solution is obtained；
（2）With peristaltic pump by concentration 7mol/L sodium hydroxide solution, concentration 6mol/L ammoniacal liquor and step（1）What is obtained is mixed Close solution to squeeze into reactor, the pH for keeping solution in reactor is 10.8, and ammonium ion concentration is 8.5, and temperature is 55 DEG C, is turned Speed is 280r/min, is shut down when reacting 35 hours by coprecipitation and reach 10.5 ± 0.2 μm to presoma particle diameter, dries, obtains To nickel-cobalt-manganese ternary precursor powder；
（3）By 20g nickel-cobalt-manganese ternaries precursor powder and 9.4g lithium carbonate powders（Lithiumation proportioning is 1.15）After well mixed, In resistance furnace, 850 DEG C are warming up to from room temperature with 5 DEG C/min of heating rate under air atmosphere, 12h is incubated in 850 DEG C；Insulation terminates After cool to room temperature with the furnace, obtain nickel cobalt manganese lithium oxide powder；
Referring to Fig. 1, obtained cobalt nickel oxide manganses lithium powder particle has become the SEM figures of obtained nickel cobalt manganese lithium oxide powder Greatly, physically well develop, and without sintered bonds together, pattern is preferable.
（4）0.16g zinc powders are dissolved in 30ml ammoniacal liquor（AR）In, settled solution is obtained, then add into settled solution 10g nickel cobalt manganese lithium oxide powders, stir, obtain suspension；
（5）Heating stirring to suspension is evaporated, then is placed in 100 DEG C of baking ovens and is dried, and obtained solid powder is hollow in resistance furnace Under gas atmosphere, 700 DEG C are warming up to 5 DEG C/min of heating rate, in 700 DEG C of insulation calcining 3h, obtain the lithium of modified zinc oxide from Sub- battery nickel-cobalt-manganternary ternary anode material.
The SEM figures of the nickel-cobalt-manganternary ternary anode material of the modified zinc oxide of preparation are as shown in fig. 4 a, spherical from Fig. 4 a Uniformly cladding has gone up one layer of atrament to particle surface, is understood compared with cobalt nickel oxide manganses lithium powder particle, particle surface has Obvious blackening, and pattern does not change preferably substantially before with uncoated.
CR2016 half-cells are made in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide of preparation, in electricity Press 4.6V, under the conditions of 1C constant current charge-discharges, 50 circulation figures of discharge and recharge as shown in Figure 4 b, from Fig. 4 b, 50 circulation volumes Conservation rate is by unmodified 79.2%（Specific discharge capacity drops to 153.1mAh/g by 188.9mAh/g）Rise to modified 96.87%（Specific discharge capacity drops to 164.1mAh/g by 169.4mAh/g）.
Embodiment 4
The preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, specifically comprises the following steps：
（1）39.43kg NiSO are taken respectively4·6H2O、16.87kg CoSO4·7H2O and 15.21kg MnSO4·H2O, add water To 150L, stirring and dissolving, 150L concentration 2mol/L mixed solution is obtained；
（2）With peristaltic pump by concentration 7mol/L sodium hydroxide solution, concentration 6mol/L ammoniacal liquor and step（1）What is obtained is mixed Close solution to squeeze into reactor, the pH for keeping solution in reactor is 10.8, and ammonium ion concentration is 8.5, and temperature is 55 DEG C, is turned Speed is 280r/min, is shut down when reacting 35 hours by coprecipitation and reach 10.5 ± 0.2 μm to presoma particle diameter, dries, obtains To nickel-cobalt-manganese ternary precursor powder；
（3）By 20g nickel-cobalt-manganese ternaries precursor powder and 9.4g lithium carbonate powders（Lithiumation proportioning is 1.15）After well mixed, In resistance furnace, 850 DEG C are warming up to from room temperature with 5 DEG C/min of heating rate under air atmosphere, 14h is incubated in 850 DEG C；Insulation terminates After cool to room temperature with the furnace, obtain nickel cobalt manganese lithium oxide powder；
Referring to Fig. 1, obtained cobalt nickel oxide manganses lithium powder particle has become the SEM figures of obtained nickel cobalt manganese lithium oxide powder Greatly, physically well develop, and without sintered bonds together, pattern is preferable.
（4）0.29g zinc gluconates are dissolved in 30mL ultra-pure waters, obtain settled solution, then add into settled solution Enter 10g nickel cobalt manganese lithium oxide powders, stir, obtain suspension；
（5）Heating stirring to suspension is evaporated, then is placed in 100 DEG C of baking ovens and is dried, and obtained solid powder is hollow in resistance furnace Under gas atmosphere, 700 DEG C are warming up to 5 DEG C/min of heating rate, in 700 DEG C of insulation calcining 3h, obtain the lithium of modified zinc oxide from Sub- battery nickel-cobalt-manganternary ternary anode material.
The SEM figures of the nickel-cobalt-manganternary ternary anode material of the modified zinc oxide of preparation are as shown in Figure 5 a, spherical from Fig. 5 a Uniformly cladding has gone up one layer of atrament to particle surface, is understood compared with cobalt nickel oxide manganses lithium powder particle, particle surface has Obvious blackening, and pattern does not change preferably substantially before with uncoated.
CR2016 half-cells are made in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide of preparation, in electricity Press 4.6V, under the conditions of 1C constant current charge-discharges, 50 circulation figures of discharge and recharge as shown in Figure 5 b, from Fig. 5 b, 50 circulation volumes Conservation rate is by unmodified 75.94%（Specific discharge capacity drops to 129.7mAh/g by 170.8mAh/g）Rise to modified 91.21%（Specific discharge capacity drops to 153.5mAh/g by 168.3mAh/g）, and discharge capacity is more unmodified first puts first Capacitance does not reduce substantially.
Embodiment 5
The preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, specifically comprises the following steps：
（1）39.43kg NiSO are taken respectively4·6H2O、16.87kg CoSO4·7H2O and 15.21kg MnSO4·H2O, add water To 150L, stirring and dissolving, 150L concentration 2mol/L mixed solution is obtained；
（2）With peristaltic pump by concentration 7mol/L sodium hydroxide solution, concentration 6mol/L ammoniacal liquor and step（1）What is obtained is mixed Close solution to squeeze into reactor, the pH for keeping solution in reactor is 10.8, and ammonium ion concentration is 8.5, and temperature is 55 DEG C, is turned Speed is 280r/min, is shut down when reacting 35 hours by coprecipitation and reach 10.5 ± 0.2 μm to presoma particle diameter, dries, obtains To nickel-cobalt-manganese ternary precursor powder；
（3）By 20g nickel-cobalt-manganese ternaries precursor powder and 9.4g lithium carbonate powders（Lithiumation proportioning is 1.15）After well mixed, In resistance furnace, 880 DEG C are warming up to from room temperature with 5 DEG C/min of heating rate under air atmosphere, 11h is incubated in 880 DEG C；Insulation terminates After cool to room temperature with the furnace, obtain nickel cobalt manganese lithium oxide powder；
Referring to Fig. 1, obtained cobalt nickel oxide manganses lithium powder particle has become the SEM figures of obtained nickel cobalt manganese lithium oxide powder Greatly, physically well develop, and without sintered bonds together, pattern is preferable.
（4）0.57g zinc gluconates are dissolved in excessive ultra-pure water, obtain settled solution, then into settled solution 10g nickel cobalt manganese lithium oxide powders are added, stirs, obtains suspension；
（5）Heating stirring to suspension is evaporated, then is placed in 100 DEG C of baking ovens and is dried, and obtained solid powder is hollow in resistance furnace Under gas atmosphere, 700 DEG C are warming up to 5 DEG C/min of heating rate, in 700 DEG C of insulation calcining 3h, obtain the lithium of modified zinc oxide from Sub- battery nickel-cobalt-manganternary ternary anode material.
The SEM figures of the nickel-cobalt-manganternary ternary anode material of the modified zinc oxide of preparation are as shown in Figure 6 a, spherical from Fig. 6 a Uniformly cladding has gone up one layer of atrament to particle surface, is understood compared with cobalt nickel oxide manganses lithium powder particle, particle surface has Obvious blackening, and pattern does not change preferably substantially before with uncoated.
CR2016 half-cells are made in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide of preparation, in electricity Press 4.6V, under the conditions of 1C constant current charge-discharges, 50 circulation figures of discharge and recharge as shown in Figure 6 b, from Fig. 6 b, 50 circulation volumes Conservation rate is by unmodified 75.94%（Specific discharge capacity drops to 129.7mAh/g by 170.8mAh/g）Rise to modified 90.79%（Specific discharge capacity drops to 152.8mAh/g by 168.3mAh/g）, and discharge capacity is more unmodified first puts first Capacitance does not reduce substantially.
Embodiment 6
The preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, specifically comprises the following steps：
（1）39.43kg NiSO are taken respectively4·6H2O、16.87kg CoSO4·7H2O and 15.21kg MnSO4·H2O, add water To 150L, stirring and dissolving, 150L concentration 2mol/L mixed solution is obtained；
（2）With peristaltic pump by concentration 7mol/L sodium hydroxide solution, concentration 6mol/L ammoniacal liquor and step（1）What is obtained is mixed Close solution to squeeze into reactor, the pH for keeping solution in reactor is 10.8, and ammonium ion concentration is 8.5, and temperature is 55 DEG C, is turned Speed is 280r/min, is shut down when reacting 35 hours by coprecipitation and reach 10.5 ± 0.2 μm to presoma particle diameter, dries, obtains To nickel-cobalt-manganese ternary precursor powder；
（3）By 20g nickel-cobalt-manganese ternaries precursor powder and 9.4g lithium carbonate powders（Lithiumation proportioning is 1.15）After well mixed, In resistance furnace, 880 DEG C are warming up to from room temperature with 5 DEG C/min of heating rate under air atmosphere, 14h is incubated in 880 DEG C；Insulation terminates After cool to room temperature with the furnace, obtain nickel cobalt manganese lithium oxide powder；
Referring to Fig. 1, obtained cobalt nickel oxide manganses lithium powder particle has become the SEM figures of obtained nickel cobalt manganese lithium oxide powder Greatly, physically well develop, and without sintered bonds together, pattern is preferable.
（4）1.14g zinc gluconates are dissolved in excessive ultra-pure water, obtain settled solution, then into settled solution 10g nickel cobalt manganese lithium oxide powders are added, stirs, obtains suspension；
（5）Heating stirring to suspension is evaporated, then is placed in 100 DEG C of baking ovens and is dried, and obtained solid powder is hollow in resistance furnace Under gas atmosphere, 700 DEG C are warming up to 5 DEG C/min of heating rate, in 700 DEG C of insulation calcining 3h, obtain the lithium of modified zinc oxide from Sub- battery nickel-cobalt-manganternary ternary anode material.
The SEM figures of the nickel-cobalt-manganternary ternary anode material of the modified zinc oxide of preparation are as shown in Figure 7a, spherical from Fig. 7 a Uniformly cladding has gone up one layer of atrament to particle surface, is understood compared with cobalt nickel oxide manganses lithium powder particle, particle surface has Obvious blackening, and pattern does not change preferably substantially before with uncoated.
CR2016 half-cells are made in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of the modified zinc oxide of preparation, in electricity Press 4.6V, under the conditions of 1C constant current charge-discharges, 50 circulation figures of discharge and recharge as shown in Figure 7b, from Fig. 7 b, 50 circulation volumes Conservation rate is by unmodified 75.94%（Specific discharge capacity drops to 129.7mAh/g by 170.8mAh/g）Rise to modified 88.1%（Specific discharge capacity drops to 147.3mAh/g by 167.2mAh/g）, and discharge capacity is more unmodified first puts first Capacitance does not reduce substantially.

Claims (10)

  1. A kind of 1. preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide, it is characterised in that including Following steps：
    （1）Nickel sulfate, cobaltous sulfate and manganese sulfate is soluble in water, it is thoroughly mixed uniformly, obtains mixed solution；
    （2）Sodium hydroxide solution and ammoniacal liquor are added into step（1）In obtained mixed solution, nickel cobalt is generated by coprecipitation reaction Manganese ternary precursor powder；
    （3）After nickel-cobalt-manganese ternary precursor powder is uniformly mixed with lithium carbonate powder, it is calcined, obtains in air or oxygen atmosphere To nickel cobalt manganese lithium oxide powder；
    （4）Zinc source power is dissolved in excessive ammonia, obtains settled solution, adds nickel cobalt manganese lithium oxide powder, stirring is equal It is even, obtain suspension；
    （5）By step（4）Obtained suspension slow evaporation is dried to being evaporated, and obtained solid powder is forged in air atmosphere Burn, obtain the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide.
  2. A kind of 2. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（1）In, the mol ratio of the nickel sulfate, cobaltous sulfate and manganese sulfate is 4 ~ 6：1.7~2：2.5~3.5； The concentration of the mixed solution is 1.5 ~ 2.5mol/L.
  3. A kind of 3. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（2）In, the concentration of the sodium hydroxide solution is 5 ~ 8mol/L；The concentration of the ammoniacal liquor be 4 ~ 7mol/L；During the coprecipitation reaction, it is 10.8 ± 0.1 to control pH value of solution, and ammonium ion concentration is 8.5 ± 0.2g/L, Temperature is 50 ~ 60 DEG C, reaction time 35h；The particle diameter D of the nickel-cobalt-manganese ternary precursor powder50For 10.5 ± 0.2 μm.
  4. A kind of 4. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（3）In, the lithiumation proportioning that the nickel-cobalt-manganese ternary precursor powder mixes with lithium carbonate powder is 1 ~ 1.3, i.e. M：Li=1:1 ~ 1.3, wherein M=Ni, Co and Mn.
  5. A kind of 5. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（3）In, the roasting is calcined 8 ~ 17 hours at 750 ~ 900 DEG C.
  6. A kind of 6. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（4）In, the zinc source includes zinc powder, zinc chloride, zinc sulfate or zinc gluconate.
  7. A kind of 7. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（4）In, the concentration of the ammoniacal liquor is 4 ~ 7mol/L.
  8. A kind of 8. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 6 Method, it is characterised in that step（4）In, the zinc source is zinc gluconate, and ammoniacal liquor is substituted using ultra-pure water.
  9. A kind of 9. preparation side of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that step（5）In, the drying is in 80 ~ 150 DEG C of drying in oven；The calcining is at 400 ~ 800 DEG C Calcining 0.5 ~ 5 hour.
  10. A kind of 10. preparation of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide according to claim 1 Method, it is characterised in that in the lithium ion battery nickel-cobalt-manganese ternary positive electrode of obtained modified zinc oxide, the quality of zinc oxide Fraction is 0.3 ~ 5%.
CN201710897989.4A 2017-09-28 2017-09-28 A kind of preparation method of the lithium ion battery nickel-cobalt-manganese ternary positive electrode of modified zinc oxide Pending CN107799741A (en)

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