CN109879331A - The nickelic tertiary cathode material and preparation method of a kind of fast-ionic conductor cladding and its lithium ion battery being prepared - Google Patents
The nickelic tertiary cathode material and preparation method of a kind of fast-ionic conductor cladding and its lithium ion battery being prepared Download PDFInfo
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Abstract
The invention discloses a kind of nickelic tertiary cathode material of fast-ionic conductor cladding and preparation method and its lithium ion batteries being prepared.The substrate of the nickelic tertiary cathode material of the fast-ionic conductor cladding is LiNi1‑x‑yCoxMnyMzO2, wherein any one or more in 0 < x≤0.15,0 < y≤0.15,0≤z≤0.1, M Al, Mg, Co, Ni, Ti, Fe, Zr, Sn；The chemical general formula of the fast-ionic conductor is Li1+aAaD2‑a(PO4)3, wherein any one or more in A Al, Cr, Ga, Fe, Sc, In, Lu, Y, La, any one or more in D Ti, Ge, Zr, Sn, Hf, wherein 0 < a≤1.The present invention, which coats the fast-ionic conductor by surface, can effectively reduce the remaining lithium on tertiary cathode material surface, and reduce the side reaction of tertiary cathode material and electrolyte；Lithium ion battery first charge-discharge specific capacity height, the capacity retention ratio assembled by positive electrode of the present invention is high.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of nickelic tertiary cathode of fast-ionic conductor cladding
Material and preparation method and its lithium ion battery being prepared.
Background technique
In recent years, environmental problem and fossil resources scarcity problem get worse the pass for having caused people to green energy resource
Note becomes whole world enterprise and scientific research institution by the electric car of power source of environmentally protective battery especially lithium ion battery
The emphasis of research.Demand with electric car to energy density lithium ion power battery increasingly increases, and nickel-cobalt-manganese ternary is just
Pole material and its derivative show wide application prospect because of higher theoretical specific capacity.
For the energy density for promoting battery, the content of nickel is constantly elevated in the modification of positive electrode, currently, nickelic
Ternary material LiNi0.6Co0.2Mn0.2O2(NCM622)、LiNi0.8Co0.1Mn0.1O2(NCM811) volume production has been realized.However, nickel contains
The rising of amount not only results in the mixing of lithium and nickel element, and will lead between particle that alkaline impurities are remaining substantially to be increased, into
And cause production gas violent in charge and discharge process, lead to battery deformation of cylindrical, recycle and shelf-life shortening, and it is hidden to generate safety
Suffer from.
In the strategy of numerous promotion ternary material cycle performances and high rate performance, surface cladding is a kind of effective side
Method.Surface cladding not only can be to avoid the interfacial reaction of active substances in cathode materials and electrolyte, but also can improve active material
Expect the dispersibility and thermal stability of particle, and then improves the electrochemical stability of positive electrode, during charge and discharge cycles, drop
Low activity substance improves capacity retention ratio because of damage suffered by structure change.
Currently used covering material is oxide, fluoride, inorganic salts, polymer etc..Wherein, oxide coats
Purpose mainly prevents positive active material from being corroded by HF, inhibits the generation of surface side reaction.In previous research, commonly use
Al2O3、TiO2、ZrO2, MgO etc. be used as coating, but the most electric conductivity of these oxides is poor, cannot be the migration of lithium ion
Enough channels are provided.Therefore it provides a kind of function of the having the above coating and high oxide of conductivity is to improve ternary
The necessary condition of material circulation performance.
Summary of the invention
The purpose of the present invention is to provide a kind of fast-ionic conductor cladding nickelic tertiary cathode material and preparation method with
And its lithium ion battery being prepared.
To achieve the goals above, the technical scheme adopted by the invention is as follows:
A kind of nickelic tertiary cathode material of fast-ionic conductor cladding, the nickelic tertiary cathode of the fast-ionic conductor cladding
The substrate of material is LiNi1-x-yCoxMnyMzO2, wherein 0 < x≤0.15,0 < y≤0.15,0≤z≤0.1, M Al, Mg, Co,
Any one or more in Ni, Ti, Fe, Zr, Sn.
The chemical general formula of the fast-ionic conductor is Li1+aAaD2-a(PO4)3, wherein A Al, Cr, Ga, Fe, Sc, In,
Any one or more in Lu, Y, La, any one or more in D Ti, Ge, Zr, Sn, Hf, wherein 0 < a≤1.
The ratio between amount of substance of the fast-ionic conductor and substrate is n, 0 < n≤0.05.
The present invention also provides the preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding, the systems
Preparation Method the following steps are included:
(1) nickel cobalt manganese hydroxide precursor is synthesized；
(2) it by nickel cobalt manganese hydroxide precursor with lithium source and the compound mechanical containing M mixes, is calcined under oxygen atmosphere
Processing obtains substrate；
(3) it is powder by fast-ionic conductor ball milling, cladding is then mixed with substrate, mixture obtains fast ion after sintering
The nickelic tertiary cathode material of conductor cladding.
Further, in step (1), the synthetic method of the nickel cobalt manganese hydroxide precursor are as follows:
Nickel salt, cobalt salt and manganese salt are dissolved in deionized water by (1-1), obtain salting liquid I；Three kinds of gold in the salting liquid I
The total concentration for belonging to salt is 1.0~2.0mol/L.
Precipitating reagent is dissolved in deionized water by (1-2), obtains precipitant solution II；Precipitating reagent in the precipitant solution II
Concentration be 5.0~10.0mol/L.
(1-3) mixes complexing agent with deionized water, obtains enveloping agent solution III；It is complexed in the enveloping agent solution III
The concentration of agent is 1~8mol/L.
Salting liquid I, precipitant solution II and tri- kinds of solution of enveloping agent solution III are injected reaction by (1-4) at the same rate
It is mixed in kettle, nickel cobalt manganese hydroxide precursor precipitating is obtained after coprecipitation reaction, presoma precipitating is filtered after ageing, is clear
It washes, and dry in vacuum drying oven.
Further, in step (1-1), the manganese in the cobalt ions and manganese salt in nickel ion, cobalt salt in the nickel salt from
The molar ratio of son is (1-x-y): x:y, 0 < x≤0.15,0 < y≤0.15.
In step (1-1), the nickel salt is nickel chloride, nickel nitrate, any one or more in nickel sulfate；The cobalt salt
For any one or more in cobalt chloride, cobalt nitrate, cobaltous sulfate；The manganese salt is manganese chloride, manganese nitrate, appointing in manganese sulfate
It anticipates one or more.
In step (1-2), the precipitating reagent is potassium hydroxide, sodium hydroxide, any one or more in lithium hydroxide.
In step (1-3), the complexing agent is ammonium hydroxide, sodium citrate, any one or more in ammonium nitrate.
In step (1-4), coprecipitation reaction temperature is 40-70 DEG C, pH value 10-12, and the time of precipitation reaction is 12-30
Hour, digestion time is 5-15 hours, and it is 70-120 DEG C that presoma, which precipitates drying temperature, and drying time is 12-24 hours, dry
Water content≤1% afterwards.
In step (2), the ratio between amount of substance of the nickel cobalt manganese hydroxide precursor and lithium source is 1:1.02~1.1；
The ratio between amount of substance of nickel, cobalt, manganese, M is (1-x-y): x:y:z, wherein 0 < x≤0.15,0 < y≤0.15,0≤z≤0.1.
In step (2), lithium source is lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium acetate, any one in lithium carbonate
Kind is a variety of；Compound containing M is in the nitrate of M, chlorate, sulfate, oxide, hydroxide, sulfide, selenides
Any one or more；
In step (2), the mechanical mixture mixes in planetary ball mill；The time of the mechanical mixture is 1-5 hours；
The calcination temperature is 700-900 DEG C, and calcination time is 12-18 hours.
In step (3), the mixing, which is coated in planetary ball mill, to be carried out；The mixing cladding time is 2-6 hours；Institute
Stating sintering temperature is 400-700 DEG C, and sintering time is 6-14 hours.
The fast-ionic conductor is synthesized using sol-gel method or high temperature solid phase synthesis.
In the sol-gel method for synthesizing fast-ionic conductor, lithium source is lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, second
Any one or more in sour lithium, phosphorus source are diammonium hydrogen phosphate, ammonium dihydrogen phosphate, any one or more in phosphoric acid, A's
Salt is any one or more in the nitrate, chlorate, acetate of Al, Cr, Ga, Fe, Sc, In, Lu, Y, La, and the salt of D is
Any one or more in the propylate of Ti, Ge, Zr, Sn, Hf, butylate；
In the high temperature solid-state method for synthesizing fast-ionic conductor, lithium source is lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, acetic acid
Any one or more in lithium, phosphorus source are diammonium hydrogen phosphate, ammonium dihydrogen phosphate, any one or more in phosphoric acid, the salt of A
For any one or more in the nitrate, chlorate, acetate of Al, Cr, Ga, Fe, Sc, In, Lu, Y, La, the compound of D
For any one or more in the oxide, hydroxide, carbonate of Ti, Ge, Zr, Sn, Hf；Temperature is calcined in high temperature solid-state method
Degree is 800 DEG C, and when sintering is 8-14 hours a length of.
The present invention also provides a kind of lithium ion cell positive, the nickelic tertiary cathode coated with the fast-ionic conductor
Material is prepared for active material.
The present invention also provides a kind of lithium ion battery, with the lithium ion cell positive in the present invention is anode assembling
At.
Compared with prior art, the present invention has the following advantages: the fast-ionic conductor ionic conductivity is higher, it ensure that and fill
The fast transferring of lithium ion in discharge process；The fast-ionic conductor is coated by surface, part lithium is empty in lithium fast-ionic conductor
The presence of position ensure that during cladding by sufficiently reacting with residual alkali, effectively reduce the remnants on tertiary cathode material surface
Lithium, and by physical barrier, reduce the side reaction of tertiary cathode material and electrolyte；The lithium assembled by positive electrode of the present invention from
Sub- battery first charge-discharge specific capacity is high, capacity retention ratio is high；Cladding process of the present invention, doping process are simple, are suitable for extensive
Production.
Detailed description of the invention
Fig. 1 is the SEM figure of the nickelic tertiary cathode material of fast-ionic conductor cladding prepared by embodiment 1.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Embodiment 1
A kind of preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding, comprising the following steps:
(1) nickel cobalt manganese hydroxide precursor is synthesized；
Nickel nitrate, cobalt nitrate and manganese nitrate are dissolved in deionized water by (1-1) according to stoichiometric ratio 8:1:1,
Obtain salting liquid I；The total concentration of three kinds of metal salts is 2.0mol/L in the solution I.
KOH powder is dissolved in deionized water by (1-2), obtains precipitant solution II；KOH in the precipitant solution II
Concentration is 6mol/L.
(1-3) mixes ammonium hydroxide with deionized water, obtains enveloping agent solution III；Ammonium hydroxide in the enveloping agent solution III
Concentration is 2mol/L.
(1-4) injects salting liquid I, precipitant solution II and enveloping agent solution III in reaction kettle simultaneously to be mixed, Xiang Fanying
Nitrogen is passed through in kettle, the pH value of control system is 11.5, obtains nickel cobalt manganese hydrogen-oxygen after coprecipitation reaction 12 hours at 55 DEG C
Compound presoma precipitating, presoma is precipitated and is filtered, and then cleaning in deionized water to washing lotion pH is 7.5, and is dried in vacuum
It is 15 hours dry at 80 DEG C in case, nickel cobalt manganese hydroxide precursor can be obtained.
(2) the nickel cobalt manganese hydroxide precursor for obtaining step (1) and lithium hydroxide powder, Al2O3Powder mixing, nickel
Cobalt manganese hydroxide precursor and lithium hydroxide powder, Al2O3The molar ratio of powder is 1:1.05:0.1, and high speed ball milling mixing 5 is small
When, mixture is calcined 15 hours at 800 DEG C in oxygen atmosphere then, obtains the nickelic positive electrode of Al doping；
(3) by fast-ionic conductor Li1.5Al0.5Ti1.5(PO4)3Ball milling is powder, the nickelic positive electrode then adulterated with Al
Mixing cladding 5 hours, the nickelic positive electrode and fast-ionic conductor Li of Al doping1.5Al0.5Ti1.5(PO4)3Molar ratio be 1:
0.02；It is then sintered 10 hours at 500 DEG C, obtains the nickelic tertiary cathode material of fast-ionic conductor cladding.The fast ion
Conductor Li1.5Al0.5Ti1.5(PO4)3The preparation method comprises the following steps: being with lithium nitrate, nine water aluminum nitrates, isopropyl titanate and ammonium dihydrogen phosphate
Raw material, according to document J.Am.Ceram.Soc., the sol-gel method in 2016,99,410-414 synthesizes Li1.5Al0.5Ti1.5
(PO4)3。
Divided using nickelic positive electrode of the scanning electron microscope to the fast-ionic conductor cladding that the present embodiment obtains
Analysis, as shown in Figure 1, the positive electrode that as can be seen from the figure this example obtains is micron-sized spherical second particle.
The nickelic positive electrode for the fast-ionic conductor cladding that the present embodiment obtains is prepared into positive plate, is then assembled into button
Formula battery, method particularly includes:
Nickelic positive electrode, conductive agent Super P and the binder Kynoar (PVDF) that fast-ionic conductor is coated
It is uniformly mixed, is dissolved in N-Methyl pyrrolidone (NMP), after magnetic agitation 6 hours, by gained with the ratio of mass ratio 90:5:5
Suspension is coated on aluminium foil, is then dried in vacuo 12 hours at 60 DEG C, tabletting is cut into the disk of diameter 14mm, with straight
The lithium piece of diameter 14mm is cathode, and 2300 microporous barrier of Celgard is diaphragm, lithium hexafluoro phosphate (LiPF6) ethyl carbonate ester+two
Methyl carbonic (EC+DMC) solution (concentration 1M) is electrolyte, and 1wt%LiNO is added in the electrolytic solution3, the dress of battery
It is completed in full of the glove box of Ar and water oxygen content lower than 0.1ppm with process.
Using new prestige battery test system in the voltage range of 2.75-4.2V, charging and discharging curve test is carried out at 25 DEG C,
Test result is as shown in table 1, from table 1 it follows that after charge and discharge 50 times, the capacity retention ratio of battery is still
94.3%.
Embodiment 2
A kind of preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding, comprising the following steps:
(1) nickel cobalt manganese hydroxide precursor is synthesized；
Nickel chloride, cobalt chloride and manganese chloride are dissolved in deionized water by (1-1) according to stoichiometric ratio 7:1.5:1.5, are obtained
To salting liquid I；The total concentration of three kinds of metal salts is 2.0mol/L in the solution I.
Sodium hydroxide powder is dissolved in deionized water by (1-2), obtains precipitant solution II；In the precipitant solution II
The concentration of sodium hydroxide is 6mol/L.
(1-3) mixes sodium citrate with deionized water, obtains enveloping agent solution III；Lemon in the enveloping agent solution III
The concentration of lemon acid sodium is 3mol/L.
(1-4) injects salting liquid I, precipitant solution II and enveloping agent solution III in reaction kettle simultaneously to be mixed, Xiang Fanying
Nitrogen is passed through in kettle, the pH value of control system is 10.5, obtains nickel cobalt manganese hydrogen-oxygen after coprecipitation reaction 18 hours at 40 DEG C
Compound presoma precipitating, presoma is precipitated and is filtered, and then cleaning in deionized water to washing lotion pH is 7.5, and is dried in vacuum
It is 12 hours dry at 100 DEG C in case, nickel cobalt manganese hydroxide precursor can be obtained.
(2) the nickel cobalt manganese hydroxide precursor for obtaining step (1) and lithium hydroxide powder, Al2O3Powder, MgO powder
Mixing, nickel cobalt manganese hydroxide precursor and lithium hydroxide powder, (Al2O3+ MgO) molar ratio be 1:1.03:0.1, clipping the ball
Mill mixing 5 hours, then calcines mixture 15 hours in oxygen atmosphere at 800 DEG C, obtain nickelic the three of Al and Mg doping
First positive electrode；
(3) by fast-ionic conductor Li1.5Al0.5Ge1.5(PO4)3Ball milling is powder, the nickelic anode then adulterated with Al and Mg
Material mixing cladding 5 hours, the nickelic positive electrode and fast-ionic conductor Li of Al and Mg doping1.5Al0.5Ge1.5(PO4)3Mole
Than being then sintered 10 hours at 500 DEG C for 1:0.05, the nickelic tertiary cathode material of fast-ionic conductor cladding is obtained.It is described
Fast-ionic conductor Li1.5Al0.5Ge1.5(PO4)3The preparation method comprises the following steps: with lithium nitrate, nine water aluminum nitrates, germanium oxide and biphosphate
Ammonium is raw material, and according to document J.Am.Ceram.Soc., the high temperature solid phase synthesis in 2016,99,410-414 is synthesized
Li1.5Al0.5Ge1.5(PO4)3, the calcination temperature in high temperature solid-state method synthetic method is 800 DEG C, and calcination time is 10 hours.
The nickelic tertiary cathode material for the fast-ionic conductor cladding that the present embodiment is obtained is according to the same method of embodiment 1
Positive plate is prepared, and is assembled into lithium ion battery in the same manner as shown in Example 1, using new prestige battery test system
In the voltage range of 2.75-4.2V, charging and discharging curve test is carried out at 25 DEG C, test result is as shown in table 1, can from table 1
To find out, after charge and discharge 50 times, the capacity retention ratio of battery is still 95.2%.
Embodiment 3
A kind of preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding, comprising the following steps:
(1) nickel cobalt manganese hydroxide precursor is synthesized according to method in the same manner as in Example 1；
(2) the nickel cobalt manganese hydroxide precursor for obtaining step (1) and lithium hydroxide powder, Al2O3Powder, MgO powder
And TiO2Powder mixing, nickel cobalt manganese hydroxide precursor and lithium hydroxide powder, (Al2O3+MgO+TiO2) molar ratio be 1:
1.06:0.08 high speed ball milling mixing 5 hours, then calcines mixture 15 hours in oxygen atmosphere at 850 DEG C, obtain Al,
The nickelic tertiary cathode material of Mg and Ti doping；
(3) by fast-ionic conductor Li1.5Al0.5Sn1.5(PO4)3Ball milling is powder, then nickelic with Al, Mg and Ti doping
Positive electrode mixing cladding 5 hours, the nickelic positive electrode and fast-ionic conductor Li of Al, Mg and Ti doping1.5Al0.5Sn1.5
(PO4)3Molar ratio be 1:0.05, then be sintered 10 hours at 500 DEG C, obtaining fast-ionic conductor coat nickelic ternary just
Pole material.The fast-ionic conductor Li1.5Al0.5Sn1.5(PO4)3The preparation method comprises the following steps: with lithium nitrate, nine water aluminum nitrates, tin oxide
It is raw material with ammonium dihydrogen phosphate, the high temperature solid phase synthesis according to document J.Am.Ceram.Soc., in 2016,99,410-414
Synthesize Li1.5Al0.5Sn1.5(PO4)3, the calcination temperature in high temperature solid-state method synthetic method is 800 DEG C, and calcination time is 12 hours.
The nickelic tertiary cathode material for the fast-ionic conductor cladding that the present embodiment is obtained is according to the same method of embodiment 1
Positive plate is prepared, and is assembled into lithium ion battery in the same manner as shown in Example 1, using new prestige battery test system
In the voltage range of 2.75-4.2V, charging and discharging curve test is carried out at 25 DEG C, test result is as shown in table 1, can from table 1
To find out, after charge and discharge 50 times, the capacity retention ratio of battery is still 95.8%.
Comparative example 1
By LiNi0.8Co0.1Mn0.1O2Positive electrode, conductive agent Super P and binder Kynoar (PVDF) are with matter
It measures the ratio than 90:5:5 to be uniformly mixed, be dissolved in N-Methyl pyrrolidone (NMP), it is after magnetic agitation 6 hours, gained is suspended
Liquid is coated on aluminium foil, is then dried in vacuo 12 hours at 60 DEG C, tabletting is cut into the disk of diameter 14mm, with diameter
The lithium piece of 14mm is cathode, and 2300 microporous barrier of Celgard is diaphragm, lithium hexafluoro phosphate (LiPF6) ethyl carbonate ester+diformazan
Base carbonic ester (EC+DMC) solution (concentration 1M) is electrolyte, and 1wt%LiNO is added in the electrolytic solution3, the assembly of battery
Process is completed in full of the glove box of Ar and water oxygen content lower than 0.1ppm.Using new prestige battery test system in 2.75-
In the voltage range of 4.2V, charging and discharging curve test is carried out at 25 DEG C, test result is as shown in table 1, from table 1 it follows that
After charge and discharge 50 times, the capacity retention ratio of battery only has 88.7%.
Comparative example 2
A kind of preparation method of the nickelic tertiary cathode material of Al doping, comprising the following steps:
(1) nickel cobalt manganese hydroxide precursor is synthesized, method is same as Example 1；
(2) by nickel cobalt manganese hydroxide precursor and lithium hydroxide powder, Al2O3Powder mixes, before nickel cobalt manganese hydroxide
Drive body and Al2O3The molar ratio of powder be 1:0.1, high speed ball milling mixing 5 hours, then by mixture 800 DEG C in oxygen atmosphere
Lower calcining 15 hours, obtains the nickelic positive electrode of Al doping.
With nickelic tertiary cathode material, conductive agent Super P and the binder Kynoar (PVDF) of Al doping with matter
It measures the ratio than 90:5:5 to be uniformly mixed, be dissolved in N-Methyl pyrrolidone (NMP), it is after magnetic agitation 6 hours, gained is suspended
Liquid is coated on aluminium foil, is then dried in vacuo 12 hours at 60 DEG C, tabletting is cut into the disk of diameter 14mm, with diameter
The lithium piece of 14mm is cathode, and 2300 microporous barrier of Celgard is diaphragm, lithium hexafluoro phosphate (LiPF6) ethyl carbonate ester+diformazan
Base carbonic ester (EC+DMC) solution (concentration 1M) is electrolyte, and 1wt%LiNO is added in the electrolytic solution3, the assembly of battery
Process is completed in full of the glove box of Ar and water oxygen content lower than 0.1ppm.Using new prestige battery test system in 2.75-
In the voltage range of 4.2V, charging and discharging curve test is carried out at 25 DEG C, test result is as shown in table 1, from table 1 it follows that
After charge and discharge 50 times, the capacity retention ratio of battery only has 90.1%.
The performance test results of table 1 Examples 1 to 3 and comparative example 1~2
From table 1 it follows that by the nickelic tertiary cathode material table of fast-ionic conductor cladding in the embodiment of the present invention
Face remnants lithium content significantly reduces, and reduces the side reaction of tertiary cathode material and electrolyte；By fast-ionic conductor cladding
Discharge capacity and capacity retention ratio are also highly improved nickelic tertiary cathode material for the first time.
A kind of above-mentioned nickelic tertiary cathode material that fast-ionic conductor is coated referring to embodiment and preparation method and its
The detailed description that the lithium ion battery being prepared carries out, is illustrative without being restrictive, can be according to limited range
Several embodiments, therefore the change and modification in the case where not departing from present general inventive concept are enumerated, protection of the invention should be belonged to
Within the scope of.
Claims (10)
1. a kind of nickelic tertiary cathode material of fast-ionic conductor cladding, which is characterized in that the height of the fast-ionic conductor cladding
The substrate of nickel tertiary cathode material is LiNi1-x-yCoxMnyMzO2, wherein 0 < x≤0.15,0 < y≤0.15,0≤z≤0.1, M are
Any one or more in Al, Mg, Co, Ni, Ti, Fe, Zr, Sn.
2. the nickelic tertiary cathode material of fast-ionic conductor according to claim 1 cladding, which is characterized in that it is described fastly from
The chemical general formula of sub- conductor is Li1+aAaD2-a(PO4)3, wherein it is any one in A Al, Cr, Ga, Fe, Sc, In, Lu, Y, La
Kind is a variety of, any one or more in D Ti, Ge, Zr, Sn, Hf, wherein 0 < a≤1.
3. the nickelic tertiary cathode material of fast-ionic conductor according to claim 1 cladding, which is characterized in that it is described fastly from
The ratio between amount of substance of sub- conductor and substrate is n, 0 < n≤0.05.
4. the preparation side of the nickelic tertiary cathode material of fast-ionic conductor cladding according to claim 1 to 3
Method, which is characterized in that the preparation method comprises the following steps:
(1) nickel cobalt manganese hydroxide precursor is synthesized；
(2) by nickel cobalt manganese hydroxide precursor with lithium source and the compound mechanical containing M mixes, the calcination processing under oxygen atmosphere
Obtain substrate；
(3) it is powder by fast-ionic conductor ball milling, cladding is then mixed with substrate, mixture obtains fast-ionic conductor after sintering
The nickelic tertiary cathode material of cladding.
5. the preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding according to claim 4, feature exist
In in step (2), the ratio between amount of substance of the nickel cobalt manganese hydroxide precursor and lithium source is 1:1.02~1.1；Nickel, cobalt,
The ratio between amount of substance of manganese, M is (1-x-y): x:y:z, wherein 0 < x≤0.15,0 < y≤0.15,0≤z≤0.1.
6. the preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding according to claim 4, feature exist
In, in step (2), lithium source be lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium acetate, in lithium carbonate any one or
It is a variety of；Compound containing M is appointing in the nitrate of M, chlorate, sulfate, oxide, hydroxide, sulfide, selenides
It anticipates one or more；The mechanical mixture mixes in planetary ball mill；The time of the mechanical mixture is 1-5 hours；It is described
Calcination temperature is 700-900 DEG C, and calcination time is 12-18 hours.
7. the preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding according to claim 4, feature exist
In in step (3), the mixing, which is coated in planetary ball mill, to be carried out；The mixing cladding time is 2-6 hours；The burning
Junction temperature is 400-700 DEG C, and sintering time is 6-14 hours.
8. the preparation method of the nickelic tertiary cathode material of fast-ionic conductor cladding according to claim 4, feature exist
In the fast-ionic conductor is synthesized using sol-gel method or high temperature solid phase synthesis.
9. a kind of lithium ion cell positive, which is characterized in that with the cladding of fast-ionic conductor described in claim 1-3 any one
Nickelic tertiary cathode material be prepared for active material.
10. a kind of lithium ion battery, which is characterized in that with lithium ion cell positive as claimed in claim 9 be anode assembling and
At.
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