CN108023077A - A kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof - Google Patents

A kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof Download PDF

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CN108023077A
CN108023077A CN201711241652.4A CN201711241652A CN108023077A CN 108023077 A CN108023077 A CN 108023077A CN 201711241652 A CN201711241652 A CN 201711241652A CN 108023077 A CN108023077 A CN 108023077A
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positive electrode
fast
ionic conductor
coating modification
nickelic positive
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胡常青
佘圣贤
袁徐俊
谢恒斌
梅文捷
于建
刘志远
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Ningbo New Energy Polytron Technologies Inc
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Ningbo New Energy Polytron Technologies Inc
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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
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof, the nickelic positive electrode includes：Base material, the base material are the compound L iNi shown in Formulas I1‑x‑ yCoxMnyMzO2；In Formulas I, 0 ＜ x≤0.20,0 ＜ y≤0.20,0 ＜ z≤0.1；The M is any one or more in Al, Mg, Ti, Zr, Mn, Ni, Sn, Co, Zn, W, Mo, Ru, Ca, Sr, Ba, B, Y, V, Nb element；The preparation method includes the following steps：Nickelic positive electrode is washed and is dried, is then uniformly mixed with appropriate covering, sintering sieving, obtains the nickelic positive electrode of fast-ionic conductor coating modification.The present invention coats fast-ionic conductor by washing and surface dry method reduces the alkali number on positive electrode surface, reduces the side reaction of material and electrolyte, improves the high-temperature stability and security of material；Fast-ionic conductor is coated by doping and surface, improves the energy density of material, high rate performance, cycle performance, ultimately increases the long circulation life of battery.

Description

A kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery anode, and in particular to a kind of fast-ionic conductor coating modification is nickelic just Pole material and preparation method thereof.
Background technology
The nickelic positive electrode LiNi of lithium ion battery1-x-yCoxMnyO2(0 ＜ x≤0.20,0 ＜ y≤0.20) and cobalt acid lithium are just Pole material, which is compared, has the advantages that specific capacity is high, cheap, under conditions of lithium battery positive and negative anodes active material is not increased, energy Battery capacity is significantly improved, is most one of positive electrode of application prospect, is widely used in mobile phone, computer etc. at present just Take the field such as formula electronic product and all kinds of green traffic instruments.But since Li, Ni ionic radius are close, prepare and use During easily occur lithium nickel mixing, its crystal structure defect is occurred, and then cause nickelic positive electrode irreversible appearance first The problems such as amount is high, and circulation decline is very fast under high voltage, high rate performance is poor.Simultaneously as nickelic positive electrode reactivity is low, system Standby material residues lithium is high, and then causes material alkalescence higher, and " jelly " phenomenon easily occurs when making pole piece, influences its pole piece and adds Work performance.In addition, with electrolyte side reaction can occur for the remaining lithium of nickelic positive electrode, easily occurs gas production under the high temperature conditions Greatly, the safety problem such as battery bulging, explosion, significantly limits widely using for nickelic positive electrode.Therefore, how cathode is reduced Side reaction between material and electrolyte, improves the stability of positive electrode during circulating battery, is to improve lithium ion battery to follow The key in ring service life.
The content of the invention
The technical problems to be solved by the invention are to overcome the technological deficiency of background technology, there is provided a kind of fast-ionic conductor bag Cover modified nickelic positive electrode and preparation method thereof.The present invention coats fast-ionic conductor by washing and surface dry method and reduces just The alkali number of pole material surface, reduces the side reaction of nickelic positive electrode and electrolyte, improves the high temperature of nickelic positive electrode Stability；Positive electrode of the present invention coats fast-ionic conductor by doping and surface, improves the energy density, forthright again of material Energy, cycle performance, ultimately increase the long circulation life of battery；The lithium ion battery prepared by the nickelic positive electrode of the present invention Specific capacity with higher, more preferable cycle performance, high rate performance and heat endurance；Present invention doping, cladding process are simple, raw Production process is easily controllable, is adapted to the scale of mass production of material.
Technological means is used by the present invention solves above-mentioned technical problem：
A kind of nickelic positive electrode of fast-ionic conductor coating modification, including：
Base material, the base material are the compound shown in Formulas I：
LiNi1-x-yCoxMnyMzO2；
In Formulas I, 0 ＜ x≤0.20,0 ＜ y≤0.20,0 ＜ z≤0.1；The M for Al, Mg, Ti, Zr, Mn, Ni, Sn, Co, Any one or more in Zn, W, Mo, Ru, Ca, Sr, Ba, B, Y, V, Nb element；
The surface of the base material is coated with coating layer；
Cladding element in the clad in including Al, Zr, Sn, Nb, Ti, V, P element any one or it is more The salt or oxide of kind.
Preferably, the base material is LiNi0.8-zCo0.1Mn0.1MzO2, 0 ＜ z≤0.1.
Preferably, the clad is LiAlO2、Li2ZrO3、Li2SnO3、LiNbO3、Li4Ti5O2、Li3V2(PO4)3In Any one or more.
Preferably, the covering used during the cladding is nanometer grade powder.
Preferably, the ratio between molal quantity of nickle cobalt lithium manganate compound in the molal quantity and base material of compound in the clad For n, 0 ＜ n≤0.1.
Preferably, the metallic element gross weight in the clad accounts for the 0.05~5% of the positive electrode gross weight.
A kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification, includes the following steps：
(1) nickel salt, cobalt salt and manganese salt are dissolved in deionized water, obtain salting liquid；Precipitating reagent is mixed with deionized water, Obtain precipitant solution；Complexing agent is mixed with deionized water, obtains enveloping agent solution；By the salting liquid, precipitant solution It is passed through in reaction kettle and mixes with enveloping agent solution cocurrent, carry out coprecipitation reaction, in overflow to ageing-washing reaction kettle, carries out Ageing, washing, centrifuge dripping, drying sieving, obtains nickel cobalt manganese hydroxide precursor；In the nickel salt in nickel ion, cobalt salt The molar ratio of manganese ion is (1-x-y) in cobalt ions and manganese salt: x: y, 0 ＜ x≤0.20,0 ＜ y≤0.20；
(2) step (1) the nickel cobalt manganese hydroxide precursor, lithium hydroxide are mixed with compound mechanical containing M, in oxygen Middle sintering in gas atmosphere, is then cooled to room temperature under oxygen atmosphere, after two pairs of rollers, crushing, sieving, obtains base material；The M For any one or more in Al, Mg, Ti, Zr, Mn, Ni, Sn, Co, Zn, W, Mo, Ru, Ca, Sr, Ba, B, Y, V, Nb element, The molar ratio of manganese ion and the M is (1-x-y) in cobalt ions, manganese salt in nickel ion, cobalt salt in the nickel salt: x: y: z, 0 ＜ x ≤ 0.20,0 ＜ y≤0.20,0 ＜ z≤0.1；
(3) it will be mixed in step (2) the base material input deionized water, continuously stir and washed, centrifuge, dry, mistake Washing drying product is obtained after sieve；
(4) step (3) the drying product is coated after mixing with covering, secondary burning is carried out after cladding Knot, is cooled to room temperature in air atmosphere, sieves, obtains the nickelic positive electrode of fast-ionic conductor coating modification；The covering The salt of any one or more or oxide in including Al, Zr, Sn, Nb, Ti, V, P element；The quality of the covering For the A% of substrate mass, 0.01 ＜ A≤5.
Preferably, in the step (1), the nickel salt is nickel sulfate, nickel nitrate, in nickel chloride any one or it is more Kind.
Preferably, in the step (1), the cobalt salt is cobaltous sulfate, cobalt nitrate, in cobalt chloride any one or it is more Kind.
Preferably, in the step (1), the manganese salt is manganese sulfate, manganese nitrate, in manganese chloride any one or it is more Kind.
Preferably, in the step (1), the concentration of metal ion is 1.0~2.5mol/L in the salting liquid, more preferably For 1.3~1.6mol/L.
Preferably, in the step (1), the concentration of the precipitant solution is 5~15mol/L, more preferably 5~ 8mol/L。
Preferably, in the step (1), the precipitating reagent is sodium hydroxide, in potassium hydroxide, lithium hydroxide, sodium carbonate Any one or more.
Preferably, in the step (1), the concentration of the enveloping agent solution is 0.1~10mol/L, more preferably 3~ 5mol/L。
Preferably, in the step (1), the complexing agent is ammonium hydroxide, in ammonium sulfate, sodium citrate, iminodiacetic acid Any one or more.
Preferably, in the step (1), reaction temperature is 40~80 DEG C during the coprecipitation reaction, more preferably 45~ 60℃。
Preferably, in the step (1), it is 10~13 that when coprecipitation reaction, which controls the pH value of reaction system, more excellent Elect 10.5~11.5 as.
Preferably, in the step (1), the coprecipitation reaction carries out under agitation, and the speed of the stirring is 100~400rpm, more preferably 200~300rpm.
Preferably, in the step (1), the ageing carries out under agitation, the speed of the stirring for 200~ 400rpm, more preferably 200~300rpm.
Preferably, in the step (1), the digestion time is 1~10h, more preferably 2~3h.
Preferably, in the step (1), the washing is carried out with the sodium hydroxide solution that concentration is 5~20mol/L.
Preferably, in the step (1), the wash time is 20~60min, more preferably 20~30min.
Preferably, in the step (1), be washed with deionized water again after the washing to filtrate pH be 7~10 when stop, after Centrifuge dripping.
Preferably, in the step (1), the drying temperature is 50~150 DEG C, more preferably 100~120 DEG C.
Preferably, in the step (1), the drying time is 8~16h, more preferably 10~12h.
Preferably, in the step (1), water content≤1% is controlled during the drying.
Preferably, in the step (1), the nickel cobalt manganese hydroxide precursor granularity D50 is 8~15 μm.
Preferably, in the step (2), the compound containing M is the carbonate containing M, the hydroxide containing M, the nitre containing M Hydrochlorate, the chlorate containing M, the sulfate containing M, any one or more in the oxide containing M.
Preferably, in the step (2), the mechanical mixture carries out in high mixer.
Preferably, in the step (2), the sintering temperature is 650~950 DEG C, more preferably 750~850 DEG C, optimal Elect 800~850 DEG C as.
Preferably, in the step (2), the sintering time is 8~15h, more preferably 10~15h, is most preferably 11 ~13h.
Preferably, in the step (2), the oxygen concentration is ＞ 95%, more preferably >=99%.
Preferably, in the step (3), the ratio of water to material during washing is (1.0~4.0): 1, more preferably (1.5~ 2)∶1；Ratio of water to material=1 refers to that the quality of deionized water and the mass ratio of base material are 1.
Preferably, in the step (3), the washing time is 15~90min, more preferably 30~40min.
Preferably, in the step (3), the drying temperature is 50~150 DEG C, more preferably 100~120 DEG C.
Preferably, in the step (4), described be blended in planetary ball mill carries out.
Preferably, in the step (4), the cladding time is 1~5h, more preferably 2~3h.
Preferably, in the step (4), the double sintering temperature is 300~650 DEG C, more preferably 500~600 DEG C.
Preferably, in the step (4), the double sintering time is 9~15h, more preferably 10~12h.
Present invention also offers a kind of lithium ion battery, the positive electrode of the lithium ion battery is above-mentioned technical proposal institute The nickelic positive electrode of fast-ionic conductor coating modification stated, or the fast ion that method described in above-mentioned technical proposal is prepared are led The nickelic positive electrode of body coating modification.
The basic principle of the present invention：
The present invention produces nickelic presoma by coprecipitation, in a constant temperature after it is mixed with lithium hydroxide, additive Sintering obtains nickelic positive electrode under degree and certain oxygen concentration atmosphere, and the positive electrode is washed, drying and processing, with drop The residual alkali content on low positive electrode surface, reduces influence of the residual alkali to chemical property, flatulence etc. to greatest extent；Thereafter by right Washing drying after positive electrode carry out fast-ionic conductor cladding, considerably improve cladding after material cycle performance, times Rate performance and security performance.
Compared with prior art, technical scheme has the following advantages that：
(1) present invention coats fast-ionic conductor by washing and surface dry method reduces the alkali number on positive electrode surface, drop The low side reaction of nickelic positive electrode and electrolyte, improves the high-temperature stability and security of nickelic positive electrode；
(2) positive electrode of the present invention by doping and surface coat fast-ionic conductor, improve material energy density, times Rate performance, cycle performance, ultimately increase the long circulation life of battery；
(3) lithium ion battery prepared by the nickelic positive electrode of the present invention has the specific capacity of higher, preferably circulation Performance, high rate performance and heat endurance.
(4) present invention doping, cladding process are simple, and production process is easily controllable, are adapted to the scale of mass production of material.
Brief description of the drawings
Fig. 1 is the nickelic positive electrode that is prepared of the embodiment of the present invention 1 and comparative example 1 300 weeks capacity of electricity 1C circulations entirely Conservation rate curve comparison figure；
Fig. 2 is that the nickelic positive electrode button electricity 0.5C/1C that the embodiment of the present invention 1 and comparative example 1 are prepared is circulated 50 weeks Capacity retention ratio curve comparison figure；
Fig. 3 is the nickelic positive electrode amplification 5000 of the fast-ionic conductor coating modification being prepared in the embodiment of the present invention 1 SEM figures again；
Fig. 4 is the nickelic positive electrode amplification 10000 of the fast-ionic conductor coating modification being prepared in the embodiment of the present invention 1 SEM figures again.
Embodiment
Content for a better understanding of the present invention, is described further with reference to specific embodiments and the drawings.Ying Li Solution, these embodiments are only used for that the present invention is further described, rather than limit the scope of the invention.In addition, it should also be understood that, After having read present disclosure, person skilled in art makes the present invention some nonessential changes or adjustment, still belongs to In protection scope of the present invention.
Raw material used in following embodiments of the present invention is commercial goods.
The present invention does not have special limitation to the preparation method of the lithium ion battery, using known to those skilled in the art The technical solution that positive electrode is prepared into lithium ion battery.
Embodiment 1
(1) nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved in deionization in the ratio that Ni, Co, Mn elemental mole ratios are 8: 1: 1 The salting liquid that metal cation total concentration is 1.5mol/L is configured in water, stirring makes it fully be uniformly mixed so as to obtain mixing salt solution；
(2) sodium hydroxide solution of 5.5mol/L and the ammonia spirit of 5mol/L, the mixing that then will be prepared are prepared respectively Salting liquid, sodium hydroxide solution and ammonia spirit cocurrent are added in reaction kettle, are carried out under 50 DEG C, the stirring condition of 200r/min Continuous coprecipitation reaction, it is 15g/L, pH=11.0 to control ammonia value in precipitation process, treats that presoma D50 reaches 11 in supernatant liquor ± 1.0, overflow is aged into aging reactor；The ageing carries out under agitation, and the speed of stirring is 200rpm, ageing Time is 2h；The sodium hydroxide solution for being 6.5mol/L with concentration after ageing washs solid product, wash time 60min, then Be washed with deionized water to filtrate pH be 8 when stop, rear centrifuge dripping；Solid product is dried under conditions of 110 DEG C, drying time For 12h, when drying, controls water content≤1%；Sieving, obtains required nickel cobalt manganese hydroxide precursor；
(3) total atom number and lithium by above-mentioned nickel cobalt manganese hydroxide precursor and lithium hydroxide according to nickel cobalt manganese host element The ratio that atomicity ratio is 1: 1.04 mixes, and puts into nano-titanium oxide, and the addition of nano-titanium oxide is the nickel cobalt manganese hydrogen The 0.2% of oxide precursor and lithium hydroxide total amount, after be uniformly mixed in high mixer high speed, in oxygen atmosphere, (oxygen is dense Spend to calcine 14h at 835 DEG C under 99%) protection, after being cooled to room temperature after two pairs of rollers, crushing, sieving, obtain base material；
(4) base material is put into deionization in the ratio of ratio of water to material 2: 1, washs centrifuge dripping after 35min, moisture releasing material 20h, 120 DEG C of drying temperature are dried in vacuum drying oven, rear sieving obtains drying material；
(5) by LiAlO2Powder and the drying material are coated in being uniformly mixed on planetary ball mill, and the cladding time is 2h, LiAlO2Powder addition is the 0.5% of the drying material quality；Material sinters 12h at 600 DEG C after cladding, is cooled to room temperature After sieve, obtain the nickelic positive electrode of fast-ionic conductor coating modification.
Using the technical solution well known to those skilled in the art that positive electrode is prepared into lithium ion battery, by embodiment The nickelic positive electrode of fast-ionic conductor coating modification obtained in 1 is assembled into button cell, and specific method is：By obtained cathode Material, acetylene black and Kynoar (PVDF) are weighed by 94: 3: 3 mass ratioes, are uniformly mixed, and NMP stirring 2h are added, into sticky Shape slurry, is uniformly coated on aluminium foil, rear 80 DEG C of vacuum bakeouts, tabletting, cuts the positive plate of a diameter of 14mm.With diameter 16mm Pour lithium slice as negative plate, using 1mol/L LiPF6+DEC/EC (volume ratio 1: 1) mixed solution as electrolyte, with poly- Celgard propylene microcellulars film is membrane, carries out being assembled into button cell in the glove box full of argon gas.
Using LAND battery test systems (CT2001A), in the voltage range of 3.0~4.3V, 25 DEG C, 0.1C discharge and recharges Under the conditions of, test above-mentioned button cell discharge first specific volume and buckle electricity cyclic curve.
The nickelic positive electrode of fast-ionic conductor coating modification obtained in embodiment 1 is carried out using scanning electron microscope Analysis, obtains its scanning electron microscope (SEM) photograph as shown in Figure 3,4.
The nickelic positive electrode surface impurity lithium content of fast-ionic conductor coating modification that testing example 1 is prepared, pH Value, the gram volume of full battery 1C, 300 weeks capacity retention ratios (see Fig. 1) of complete electricity 1C circulations, button cell 0.1C specific discharge capacities and Detain electricity 0.5C/1C and circulate 50 weeks capacity retention ratios (see Fig. 2), test result is as shown in table 1.
Comparative example 1
(1) nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved in deionization in the ratio that Ni, Co, Mn elemental mole ratios are 8: 1: 1 The salting liquid that metal cation total concentration is 1.5mol/L is configured in water, stirring makes it fully be uniformly mixed so as to obtain mixing salt solution；
(2) sodium hydroxide solution of 5.5mol/L and the ammonia spirit of 5mol/L, the mixing that then will be prepared are prepared respectively Salting liquid, sodium hydroxide solution and ammonia spirit cocurrent are added in reaction kettle, are carried out under 50 DEG C, the stirring condition of 200r/min Continuous coprecipitation reaction, it is 15g/L, pH=11.0 to control ammonia value in precipitation process, treats that presoma D50 reaches 11 in supernatant liquor ± 1.0, overflow is aged into aging reactor；The ageing carries out under agitation, and the speed of stirring is 200rpm, ageing Time is 2h；The sodium hydroxide solution for being 6.5mol/L with concentration after ageing washs solid product, wash time 60min, then Be washed with deionized water to filtrate pH be 8 when stop, rear centrifuge dripping；Solid product is dried under conditions of 110 DEG C, drying time For 12h, when drying, controls water content≤1%；Sieving, obtains required nickel cobalt manganese hydroxide precursor；
(3) total atom number and lithium by above-mentioned nickel cobalt manganese hydroxide precursor and lithium hydroxide according to nickel cobalt manganese host element The ratio that atomicity ratio is 1: 1.04 mixes, and is uniformly mixed in high mixer high speed, in oxygen atmosphere (oxygen concentration 99%) 14h is calcined at 835 DEG C under protection, after being cooled to room temperature after two pairs of rollers, crushing, sieving, obtains nickelic positive electrode.
Using LAND battery test systems (CT2001A), in the voltage range of 3.0~4.3V, 25 DEG C, 0.1C discharge and recharges Under the conditions of, test above-mentioned button cell discharge first specific volume and buckle electricity cyclic curve.
The nickelic positive electrode surface impurity lithium content of fast-ionic conductor coating modification that test comparison example 1 is prepared, pH Value, the gram volume of full battery 1C, 300 weeks capacity retention ratios (see Fig. 1) of complete electricity 1C circulations, button cell 0.1C specific discharge capacities and Detain electricity 0.5C/1C and circulate 50 weeks capacity retention ratios (see Fig. 2), test result is as shown in table 1.
The physics and chemistry for the nickelic positive electrode that 1 embodiment 1 of table is prepared with comparative example 1, electric performance test result
As shown in Table 1, compared with nickelic positive electrode prepared by conventional method, the fast ion of the offer of the embodiment of the present invention 1 The nickelic positive electrode surface residual alkali compounds of conductor coating modification significantly reduces, improve positive electrode heat endurance and Security, while with being coated on the fast-ionic conductor collective effect on positive electrode surface, hence it is evident that improve gram appearance of positive electrode Amount, cycle performance, also improve the high rate performance of positive electrode, so that fast-ionic conductor bag prepared by the embodiment of the present invention 1 Covering modified nickelic positive electrode has more preferable energy density, high rate performance, cycle performance and heat endurance.
Described above is not the limitation to invention, and the present invention is also not limited to the example above.The common skill of the art Art personnel are in the essential scope of invention, and the variations, modifications, additions or substitutions made should also belong to protection scope of the present invention.

Claims (10)

1. a kind of nickelic positive electrode of fast-ionic conductor coating modification, it is characterised in that the fast-ionic conductor coating modification is high Nickel positive electrode, including：
Base material, the base material are the compound shown in Formulas I：
LiNi1-x-yCoxMnyMzO2；
In Formulas I, 0 ＜ x≤0.20,0 ＜ y≤0.20,0 ＜ z≤0.1；The M for Al, Mg, Ti, Zr, Mn, Ni, Sn, Co, Zn, W, any one or more in Mo, Ru, Ca, Sr, Ba, B, Y, V, Nb element；
The surface of the base material is coated with coating layer；
Any one or more of cladding element in including Al, Zr, Sn, Nb, Ti, V, P element in the clad Salt or oxide.
A kind of 2. nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 1, it is characterised in that the cladding The covering of Shi Caiyong is nanometer grade powder, nickle cobalt lithium manganate compound in the molal quantity and base material of compound in the clad The ratio between molal quantity be n, 0 ＜ n≤0.1；Metallic element gross weight in the clad accounts for the 0.05 of the positive electrode gross weight ~5%.
3. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification, it is characterised in that include the following steps：
(1) nickel salt, cobalt salt and manganese salt are dissolved in deionized water, obtain salting liquid；Precipitating reagent is mixed with deionized water, is obtained Precipitant solution；Complexing agent is mixed with deionized water, obtains enveloping agent solution；By the salting liquid, precipitant solution and network Mixture solution cocurrent, which is passed through in reaction kettle, to be mixed, progress coprecipitation reaction, in overflow to ageing-washing reaction kettle, be aged, Washing, centrifuge dripping, drying sieving, obtains nickel cobalt manganese hydroxide precursor；Cobalt ions in nickel ion, cobalt salt in the nickel salt And the molar ratio of manganese ion is (1-x-y) in manganese salt: x: y, 0 ＜ x≤0.20,0 ＜ y≤0.20；
(2) step (1) the nickel cobalt manganese hydroxide precursor, lithium hydroxide are mixed with compound mechanical containing M, in oxygen gas Middle sintering in atmosphere, is then cooled to room temperature under oxygen atmosphere, after two pairs of rollers, crushing, sieving, obtains base material；The M is Any one or more in Al, Mg, Ti, Zr, Mn, Ni, Sn, Co, Zn, W, Mo, Ru, Ca, Sr, Ba, B, Y, V, Nb element, institute State nickel ion in nickel salt, the molar ratio of manganese ion and the M is (1-x-y) in cobalt ions, manganese salt in cobalt salt: x: y: z, 0 ＜ x≤ 0.20,0 ＜ y≤0.20,0 ＜ z≤0.1；
(3) it will be mixed in step (2) base material input deionized water, continuously stir and washed, after centrifuging, dry, sieving Obtain washing drying product；
(4) step (3) the drying product is coated after mixing with covering, double sintering is carried out after cladding, It is cooled to room temperature under air atmosphere, sieves, obtain the nickelic positive electrode of fast-ionic conductor coating modification；The covering is selected from bag Include the salt of any one or more or the oxide in Al, Zr, Sn, Nb, Ti, V, P element；The quality of the covering is base material The A% of quality, 0.01 ＜ A≤5.
4. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (1), the concentration of metal ion is 1.0~2.5mol/L in the salting liquid；The precipitant solution it is dense Spend for 5~15mol/L；The concentration of the enveloping agent solution is 0.1~10mol/L.
5. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (1), reaction temperature is 40~80 DEG C during the coprecipitation reaction；Reaction is controlled during the coprecipitation reaction The pH value of system is 10~13；The coprecipitation reaction carries out under agitation, the speed of the stirring for 100~ 400rpm。
6. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (1), the ageing carries out under agitation, and the speed of the stirring is 200~400rpm；It is described old The change time is 1~10h；The washing is carried out with the sodium hydroxide solution that concentration is 5~20mol/L；The wash time is 20 ~60min；Be washed with deionized water again after the washing to filtrate pH be 7~10 when stop, rear centrifuge dripping；The drying temperature For 50~150 DEG C；The drying time is 8~16h；Water content≤1% is controlled during the drying.
7. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (2), the sintering temperature is 650~950 DEG C, and the sintering time is 8~15h, and the oxygen concentration is >95%.
8. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (3), the ratio of water to material during washing is (1.0~4.0): 1.
9. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (3), the washing time is 15~90min, and the drying temperature is 50~150 DEG C.
10. a kind of preparation method of the nickelic positive electrode of fast-ionic conductor coating modification as claimed in claim 3, its feature exist In in the step (4), described be blended in planetary ball mill carries out, and the cladding time is 1~5h, the double sintering Temperature is 300~650 DEG C, and the double sintering time is 9~15h.
CN201711241652.4A 2017-11-30 2017-11-30 A kind of nickelic positive electrode of fast-ionic conductor coating modification and preparation method thereof Pending CN108023077A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1154116A (en) * 1997-08-05 1999-02-26 Shin Kobe Electric Mach Co Ltd Alkaline storage battery nickel sintered base plate, alkaline storage battery nickel electrode plate and manufacture thereof
CN1773763A (en) * 2004-11-08 2006-05-17 深圳市比克电池有限公司 Lithium ion secondary cell with nickel-base anode active material and producing method thereof
US20110281176A1 (en) * 2008-01-17 2011-11-17 Seymour Fraser W Nanoscale intercalation materials on carbon powder, process for production, and use thereof
CN103367736A (en) * 2012-04-06 2013-10-23 协鑫动力新材料（盐城）有限公司 Surface clad lithium ion battery positive material precursor, and preparation method and application thereof
CN106505193A (en) * 2017-01-12 2017-03-15 宁波金和锂电材料有限公司 Monocrystalline nickel-cobalt lithium manganate cathode material and preparation method thereof and lithium ion battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1154116A (en) * 1997-08-05 1999-02-26 Shin Kobe Electric Mach Co Ltd Alkaline storage battery nickel sintered base plate, alkaline storage battery nickel electrode plate and manufacture thereof
CN1773763A (en) * 2004-11-08 2006-05-17 深圳市比克电池有限公司 Lithium ion secondary cell with nickel-base anode active material and producing method thereof
US20110281176A1 (en) * 2008-01-17 2011-11-17 Seymour Fraser W Nanoscale intercalation materials on carbon powder, process for production, and use thereof
CN103367736A (en) * 2012-04-06 2013-10-23 协鑫动力新材料（盐城）有限公司 Surface clad lithium ion battery positive material precursor, and preparation method and application thereof
CN106505193A (en) * 2017-01-12 2017-03-15 宁波金和锂电材料有限公司 Monocrystalline nickel-cobalt lithium manganate cathode material and preparation method thereof and lithium ion battery

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