CN108321380A - A kind of nickelic ternary anode material of lithium battery and preparation method of gallium oxide cladding - Google Patents
A kind of nickelic ternary anode material of lithium battery and preparation method of gallium oxide cladding Download PDFInfo
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Abstract
The present invention proposes a kind of nickelic ternary anode material of lithium battery and preparation method of gallium oxide cladding, nickelic tertiary cathode persursor material is prepared by coprecipitation first, persursor material is placed in soaking and stirring in boiling water later, gallium is added dropwise, until presoma surface is coated completely by white gum object, with lithium source mixing and ball milling after filtering, quickly calcining obtains the nickelic ternary anode material of lithium battery that gallium oxide coats after heating.The present invention overcomes existing oxide surface clad can not the effective defect that is regulated and controled of presoma remained on surface alkali content, be the γ Ga with defect spinel structure by gallium hydroxide gel decomposition2O3, solid solution is formed with lithium source and the residual alkali on presoma surface, inhibits the corrosion of the residual alkali content and electrolyte on surface to electrode.Further in charge and discharge process, solid solution serves as the effect of the inorganic lithium source inside SEI films, not will produce the substance of the easy aerogenesis such as lithium carbonate, to improve the high-temperature stability of nickelic tertiary cathode material.
Description
Technical field
The present invention relates to field of lithium ion battery material, and in particular to a kind of nickelic ternary lithium battery of gallium oxide cladding is just
Pole material and preparation method.
Background technology
Along with economic globalization process and energy demand it is continuous surging, find new energy storage device and have become newly
The focus of attention of energy related field.Lithium ion battery and traditional accumulator are comparatively, not only energy higher, discharge capability
Stronger, cycle life is longer, and its energy storage efficiency can be more than 90%, and the above feature determines lithium ion battery in electronic vapour
Vehicle, storage power supply etc. great development prospect.Current commercialized power-type lithium ion battery is mainly cobalt acid lithium, mangaic acid
Lithium, LiFePO4 and nickel-cobalt-manganese ternary battery.Wherein ternary battery is increasingly becoming main product due to its higher capacity, but holds
Amount is still difficult to meet the higher and higher performance requirement of electric vehicle.
Study on the modification for ternary battery is the mainstream of existing market, using high ni-type ternary battery as core direction.Three
First positive electrode LiNi1-x-yCoxMnyO2（NCM）Crystal belongs to hexagonal crystal system, is α-NaFeO2Layer structure, since its is excellent
Characteristic is increasingly becoming the mainstream selection of anode material for lithium-ion batteries, wherein for the nickelic tertiary cathode material of high power capacity
LiNi1-x-yCoxMnyO2（Molar fraction >=0.6 of Ni) research it is the most extensive, high ni-type ternary battery since nickel content is higher,
Battery capacity further increases, but the nickel lithium mixing phenomenon and unstability brought therewith are more obvious, thus has kept in check this
Application of the material in practical high-power electric device.
It is more deep for the unstability research under its high temperature at present, most important electrolyte lithium salt in lithium ion battery
For LiPF6It is very sensitive to the water of trace.LiPF6Thermal stability it is poor, it is easy to decompose and water reaction generate HF, HF
Positive electrode can be corroded, cause the dissolving of metal ion in material, material structure is destroyed, to make material electrochemical performance become
Difference.With the increase of nickel content, the lithium ion of the surface migration of active material easily forms lithium carbonate with the carbonate of attachment, increases
Add the loss of irreversible capacity, and the lithium carbonate decomposition under high temperature inside SEI films causes SEI films to fall off, and easily causes battery
Flatulence has prodigious security risk.Therefore there is highly important reality for the corrosion resistance of electrode and stability study
Meaning.
Since the electrode reaction of lithium ion battery is happened at electrode/electrolyte interface, by carrying out surface to ternary material
Coating modification is to improve another effective ways of its chemical property.Clad can prevent material of main part directly and electrolyte
Contact improves its capacity retention ratio, improves high rate performance to enhance thermal stability, corrosion resistance.But clad is to electric polarity
The influence of energy is highly dependent on performance, content, treatment conditions of clad etc..
Chinese invention patent application number：201310693297.X disclosing a kind of monocrystalline tertiary cathode material of cladding ZnO
Preparation method weighs lithium carbonate, ternary precursor and magnesia, batch mixing；It is sintered in air atmosphere；It is broken, obtain sample one；
Weigh lithium carbonate, cobalt oxide, magnesia, batch mixing；It is sintered in air atmosphere；It is broken, obtain sample two；Weigh sample one, sample
Product two and titanium dioxide, batch mixing；It is sintered in air atmosphere；It is crushed after taking-up, obtains i.e. final product mix.Chinese invention
Number of patent application 201310549937.X discloses a kind of preparation method of alumina composite nickel-cobalt lithium manganate ternary material, uses
The soluble salt of Ni, Co, Mn, ammonium hydroxide are complexing agent, and sodium hydroxide, sodium carbonate, ammonium hydrogen carbonate are precipitating reagent, are closed by being co-precipitated
At complex ternary presoma, then the soluble salt solutions of aluminium are added drop-wise in synthesized precursor solution, carry out liquid phase packet
It covers, is evenly coated impalpable structure film layer aluminium oxide on ternary material surface, reduces material charging/discharging voltage pressure difference, improve
The high rate performance and high-temperature behavior of material.
The above-mentioned cladding using oxides such as aluminium oxide can reduce contact of the electrode with electrolyte to effectively reduce electricity
Corrosion of the liquid to electrode is solved, its structural instability can be inhibited to a certain extent, but lack for presoma remained on surface
The control of alkali content and high temperature aerogenesis is difficult to keep electrode material rock-steady structure under the high temperature conditions.It is therefore proposed that one kind has
The surface cladding scheme of effect can effectively reduce corrosion of the electrolyte to electrode, solve its presoma remained on surface alkali content, inhibit
The problem of battery high-temperature aerogenesis, has highly important practical meaning to improving nickelic ternary electrode material structure high-temperature stability
Justice.
Invention content
For existing oxide surface clad can not the effective defect that is regulated and controled of presoma remained on surface alkali content, this
Invention proposes a kind of nickelic ternary anode material of lithium battery and preparation method of gallium oxide cladding, passes through gallium hydroxide gel decomposition
For the Y-Ga with defect spinel structure2O3, solid solution is formed with lithium source and the residual alkali on presoma surface, inhibits electrolyte pair
The corrosion of electrode, and the substance for the easy aerogenesis such as not will produce lithium carbonate, lithium hydroxide, to improve the high temperature of positive electrode
Stability.
To solve the above problems, the present invention uses following technical scheme：
On the one hand a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding is provided, which is characterized in that tool
Preparation is：
（1）Use soluble nickel salt, cobalt salt, manganese salt for raw material, according to nickel, the molar ratio 1-x-y of cobalt, manganese:x:Y weighs the nickel
Salt, cobalt salt, manganese salt, and the nickel salt, cobalt salt, manganese salt are added in blender, high-speed stirred is uniformly mixed, obtains mixed powder
Material, wherein 0.5<1-x-y<1,0<X≤0.2,0<y≤0.2；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, precipitation is added into the mixed solution
Agent after stirring evenly, adjusts pH=11-12, obtains nickelic ternary precursor lotion, persursor material is obtained by spray drying；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, obtains the presoma of gallium oxide package；
（4）Ball mill is added with the lithium source in the presoma that the gallium oxide is wrapped up, uniform by ball milling mixing, takes out powder
Body quickly heats up to 400-450 DEG C of heat preservation 2-5h, is warming up to calcines 4-5h at 700-720 DEG C later under oxygen-enriched environment,
After natural cooling, the nickelic ternary anode material of lithium battery of gallium oxide cladding is obtained.
Preferably, the nickel salt is one kind in nickel chloride, nickelous carbonate, nickel nitrate, nickel sulfate, nickelous bromide, nickel fluoride, institute
It is one kind in cobalt chloride, cobalt carbonate, cobalt nitrate, cobaltous sulfate, cobalt acid sodium, cobaltous bromide, cobaltous fluoride to state cobalt salt, and the manganese salt is chlorine
Change one kind in manganese, manganese carbonate, manganese nitrate, manganese sulfate, manganous bromide, manganous fluoride.
Preferably, the precipitating reagent is the mixed solution of sodium hydroxide and ammonium hydroxide, a concentration of 0.9- of sodium hydroxide
1.5mol/L, ammonia concn 2mol/L.
Preferably, in the mixed solution, a concentration of 0.3-2.1mol/L of nickel salt is controlled.
Preferably, the size of the persursor material is 8-40 microns.
Preferably, the presoma of the gallium oxide cladding, gallium oxide coating thickness are 0.08-0.20 μm.
Preferably, control ball milling speed is 260-1200rpm, Ball-milling Time 30-50min.
Preferably, step（4）Described in oxygen-enriched environment be oxygen content be 30-60%, and control carbon dioxide and other
The concentration of sour gas is less than 0.09 ‰.
Preferably, step（4）Described in the heating rate that quickly heats be 30-60 DEG C/min.
On the other hand a kind of nickelic ternary anode material of lithium battery of gallium oxide cladding is provided, by above method preparation
At.
For existing oxide surface coating technology can not for the defect that presoma remained on surface alkali content is controlled,
The present invention proposes a kind of nickelic ternary anode material of lithium battery and preparation method of gallium oxide cladding, first by being co-precipitated legal system
Standby nickelic NCM anodes persursor material, is placed in soaking and stirring in boiling water by persursor material later, gallium is added dropwise, directly
It is coated by white gum object to presoma surface, with lithium source lithia or lithium hydroxide mixing and ball milling after filtering, quickly adds completely
Heat is warming up at 700 DEG C to 400 DEG C of heat preservation 2h and calcines 4h later, and the nickelic ternary lithium electricity of gallium oxide cladding is obtained after cooling
Pond positive electrode.The lithium source is lithia or lithium hydroxide.It is with defect spinelle knot by gallium hydroxide gel decomposition
γ-the Ga of structure2O3, solid solution is formed with lithium source and the residual alkali on presoma surface, inhibits corrosion of the electrolyte to electrode.In charge and discharge
In electric process, solid solution serves as the effect of the inorganic lithium source inside SEI films, not will produce the easy production such as lithium carbonate, lithium hydroxide
The substance of gas, to improve the high-temperature stability of positive electrode.
The present invention provides a kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method, with the prior art
It compares, the feature and excellent effect protruded is：
1, the present invention prepares a kind of nickelic ternary anode material of lithium battery of gallium oxide cladding, is prepared by coprecipitation nickelic
NCM anode persursor materials, are placed in soaking and stirring in boiling water by persursor material later, gallium are added dropwise, until forerunner
Body surface face is coated completely by white gallium hydroxide jelly, with lithium source mixing and ball milling after filtering, passes through gallium hydroxide gel decomposition
For the γ-Ga with defect spinel structure2O3, solid solution is formed with lithium source and the residual alkali on presoma surface, is on the one hand coated
Layer can effectively inhibit the increase of interface impedance, inhibit corrosion of the electrolyte to electrode.On the other hand, in charge and discharge process,
Solid solution serves as the effect of the inorganic lithium source inside SEI films, not will produce the substance of the easy aerogenesis such as lithium carbonate, lithium hydroxide,
To improve the high-temperature stability of positive electrode.
2, the nickelic anode material of lithium battery process program of gallium oxide cladding of the present invention is simply controllable, and it is steady to prepare material property
It is fixed, prepared by popularization to nickelic lithium battery material and provides new way.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）According to the molar ratio 8 of nickel, cobalt, manganese:1.5:0.5 weighs nickel sulfate, cobaltous sulfate, manganese sulfate, and by nickel sulfate, sulfuric acid
Cobalt, manganese sulfate are added in blender, and high-speed stirred is uniformly mixed, obtains mixed powder；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, controls a concentration of 0.3mol/ of nickel salt
L, to the mixed solution of the mixed solution and dripping sodium hydroxide and ammonium hydroxide, a concentration of 1.5mol/L of sodium hydroxide, ammonium hydroxide
A concentration of 2mol/L adjusts pH=11, is stirred continuously, and reaction after a certain period of time, obtains nickelic ternary precursor lotion, aged,
Filtering, gained precipitation are washed repeatedly with deionized water, and the persursor material that size is 8 microns is obtained by spray drying；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, is cleaned by deionized water, and the presoma of gallium oxide package is obtained after dry；Gallium oxide coating thickness
It is 0.08 μm；
（4）The presoma that the gallium oxide is wrapped up is with lithia according to molar ratio nickel：Lithium=0.8:1 is added ball mill, control ball
Mill speed is 1200rpm, and Ball-milling Time 30min, taking-up powder uniform by ball milling mixing is 60% in oxygen content, and
Under oxygen-enriched environment of the concentration less than 0.09 ‰ for controlling carbon dioxide and other sour gas, setting heating rate is 30 DEG C/min
400 DEG C of heat preservation 2h are heated to, is warming up to later at 700 DEG C and calcines 4h, after natural cooling, obtain nickelic the three of gallium oxide cladding
First anode material of lithium battery.
The gallium oxide made from the present embodiment coats by 0.9 kilogram respectively nickelic tertiary cathode powder, 0.15 kilogram it is viscous
Tie agent Kynoar（PVDF）It is uniform with 0.15 kilogram of acetylene black mixed grinding, 9 kilograms of N-Methyl pyrrolidones are added, stir
It mixes to form uniform anode sizing agent.The anode sizing agent is coated uniformly on 20 microns of aluminium foil, is then dried at 60 DEG C, rushed
A diameter of 1cm is made in piece2Positive disk, by drying working electrode is made.Cathode use amorphous carbon material, poly- third
Alkene film is diaphragm, 1M LiPF 6/(EC+DMC) (1:1) it is that electrolyte is assembled into battery.It is filled to battery progress constant current is made
Discharge test, for voltage range between 2.5 ~ 4.6V, the discharge capacity for recording battery is as shown in table 1.
Embodiment 2
（1）According to the molar ratio 8 of nickel, cobalt, manganese:1.5:0.5 weighs nickel chloride, cobalt chloride, the raw material that manganese chloride is positive electrode,
And nickel chloride, cobalt chloride, manganese chloride are added in blender, high-speed stirred is uniformly mixed, obtains mixed powder；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, controls a concentration of 1.3mol/ of nickel salt
L, to the mixed solution of the mixed solution and dripping sodium hydroxide and ammonium hydroxide, a concentration of 0.9mol/L of sodium hydroxide, ammonium hydroxide
A concentration of 2mol/L adjusts pH=11, is stirred continuously, and reaction after a certain period of time, obtains nickelic ternary precursor lotion, aged,
Filtering, gained precipitation are washed repeatedly with deionized water, and the persursor material that size is 20 microns is obtained by spray drying；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, is cleaned by deionized water, and the presoma of gallium oxide package is obtained after dry；Gallium oxide coating thickness
It is 0.1 μm；
（4）The presoma that the gallium oxide is wrapped up is with lithia according to molar ratio nickel：Lithium=0.8:1 is added ball mill, control ball
Mill speed is 1200rpm, and Ball-milling Time 35min, taking-up powder uniform by ball milling mixing is 35% in oxygen content, and
Under oxygen-enriched environment of the concentration less than 0.09 ‰ for controlling carbon dioxide and other sour gas, setting heating rate is 45 DEG C/min
420 DEG C of heat preservation 2h are heated to, is warming up to later at 700 DEG C and calcines 5h, after natural cooling, obtain nickelic the three of gallium oxide cladding
First anode material of lithium battery.
Embodiment 3
（1）According to the molar ratio 8 of nickel, cobalt, manganese:1:1 weighs nickel nitrate, cobalt nitrate, the raw material that manganese nitrate is the positive electrode,
And nickel nitrate, cobalt nitrate, manganese nitrate are added in blender, high-speed stirred is uniformly mixed, obtains mixed powder；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, controls a concentration of 1.6mol/ of nickel salt
L, to the mixed solution of the mixed solution and dripping sodium hydroxide and ammonium hydroxide, a concentration of 1.2mol/L of sodium hydroxide, ammonium hydroxide
A concentration of 2mol/L adjusts pH=12, is stirred continuously, and reaction after a certain period of time, obtains nickelic ternary precursor lotion, aged,
Filtering, gained precipitation are washed repeatedly with deionized water, and the nickelic ternary precursor that size is 40 microns is obtained by spray drying
Material；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, is cleaned by deionized water, and the presoma of gallium oxide package is obtained after dry；Gallium oxide coating thickness
It is 0.20 μm；
（4）The presoma that the gallium oxide is wrapped up is with lithium hydroxide according to molar ratio nickel：Lithium=0.8:1 is added ball mill, control
Ball milling speed is 400rpm, and Ball-milling Time 38min, taking-up powder uniform by ball milling mixing is 55% in oxygen content, and
Under oxygen-enriched environment of the concentration less than 0.09 ‰ for controlling carbon dioxide and other sour gas, setting heating rate is 50 DEG C/min
400 DEG C of heat preservation 2h are heated to, is warming up to later at 700 DEG C and calcines 4h, after natural cooling, obtain nickelic the three of gallium oxide cladding
First anode material of lithium battery.
Embodiment 4
（1）According to the molar ratio 8 of nickel, cobalt, manganese:1.2:0.8 weighs nickel fluoride, cobaltous fluoride, manganous fluoride as the positive electrode
Raw material, and nickel fluoride, cobaltous fluoride, manganous fluoride are added in blender, high-speed stirred is uniformly mixed, obtains mixed powder；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, controls a concentration of 2.1mol/ of nickel salt
L, to the mixed solution of the mixed solution and dripping sodium hydroxide and ammonium hydroxide, a concentration of 0.9mol/L of sodium hydroxide, ammonium hydroxide
A concentration of 2mol/L adjusts pH=12, is stirred continuously, and reaction after a certain period of time, obtains nickelic ternary precursor lotion, aged,
Filtering, gained precipitation are washed repeatedly with deionized water, and the persursor material that size is 20 microns is obtained by spray drying；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, is cleaned by deionized water, and the presoma of gallium oxide package is obtained after dry；Gallium oxide coating thickness
It is 0.15 μm；
（4）The presoma that the gallium oxide is wrapped up is with lithium hydroxide according to molar ratio nickel：Lithium=0.8:1 is added ball mill, control
Ball milling speed is 700rpm, and Ball-milling Time 40min, taking-up powder uniform by ball milling mixing is 60% in oxygen content, and
Under oxygen-enriched environment of the concentration less than 0.09 ‰ for controlling carbon dioxide and other sour gas, setting heating rate is 35 DEG C/min
400 DEG C of heat preservation 5h are heated to, is warming up to later at 700 DEG C and calcines 4h, after natural cooling, obtain nickelic the three of gallium oxide cladding
First anode material of lithium battery.
Embodiment 5
（1）According to the molar ratio 6 of nickel, cobalt, manganese:2:2 weigh nickel sulfate, cobalt carbonate, the raw material that manganese carbonate is the positive electrode,
And nickel sulfate, cobalt carbonate, manganese carbonate are added in blender, high-speed stirred is uniformly mixed, obtains mixed powder；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, controls a concentration of 2.1mol/ of nickel salt
L, to the mixed solution of the mixed solution and dripping sodium hydroxide and ammonium hydroxide, a concentration of 0.9mol/L of sodium hydroxide, ammonium hydroxide
A concentration of 2mol/L adjusts pH=12, is stirred continuously, and reaction after a certain period of time, obtains nickelic ternary precursor lotion, aged,
Filtering, gained precipitation are washed repeatedly with deionized water, and the persursor material that size is 15 microns is obtained by spray drying；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, is cleaned by deionized water, and the presoma of gallium oxide package is obtained after dry；Gallium oxide coating thickness
It is 0.2 μm；
（4）The presoma that the gallium oxide is wrapped up is with lithium hydroxide according to molar ratio nickel：Lithium=0.8:1 is added ball mill, control
Ball milling speed is 1000rpm, and Ball-milling Time 50min, taking-up powder uniform by ball milling mixing is 45% in oxygen content, and
And control under oxygen-enriched environment of the concentration less than 0.09 ‰ of carbon dioxide and other sour gas, setting heating rate is 60 DEG C/
Min is heated to 400 DEG C of heat preservation 2-5h, is warming up to later at 710 DEG C and calcines 4h, after natural cooling, obtains gallium oxide cladding
Nickelic ternary anode material of lithium battery.
Comparative example 1
The LiNi of cladding processing is not carried out0.8Co0.15Mn0.05O2As ternary positive electrode active material, according to 1 identical side of embodiment
Method is prepared into battery, and test condition is consistent with embodiment 1-5, and obtaining test data, the results are shown in Table 2.
Comparative example 2
（1）It is 8 by nickel, cobalt, manganese molar ratio：1.5：0.5, the nitrate of nickel cobalt manganese is weighed in conical flask, and distilled water is added,
It is configured to solution A.
（2）It presses（Ni+Co+Mn）：NH4HCO3=1：6.5 molar ratio weighs precipitating reagent ammonium hydrogen carbonate in another conical flask,
It is configured to solution B.
（3）Solution A and solution B instill in flask, and ammonium hydroxide is at the same time added dropwise, and control ammonium hydroxide rate of addition is 5
Drop/5min.After solution A and solution B drip, the air being continuing in nitrogen displacement flask keeps micro-positive pressure
0.03MPa.After reacting 12h, stop stirring.
（4）Al in molar ratio：NH4HCO3 =0.0065 configuration aluminum sulfate solution C, flask is placed in 50 DEG C of water-baths, is used
C solution is added dropwise to flask in dropping funel, and pH value is made to be more than 8.Continue to stir 2 h, still aging 24 h after being added dropwise.
（5）It will（4）In obtained product be separated by solid-liquid separation, by obtained solid distilled water filtering and washing 5 times, then
6h is dried in vacuo at 100 DEG C to get to presoma.It presses（Ni+Co+Mn）：Li molar ratios 1：1.1 weigh lithium nitrate and presoma
3 h of ethanol in proper amount wet ball grinding is added in mixing, and then in 950 DEG C of 10 h of calcining of Muffle furnace, alumina-coated is obtained after cooling
Tertiary cathode material LiNi0.8Co0.15Mn 0.05O2。
The tertiary cathode material that embodiment 1-5, comparative example 1-2 are obtained is according to the unified manufacture craft according to embodiment 1
Test battery is prepared with method, respectively by 0.9 kilogram of tertiary cathode powder, 0.15 kilogram of binder Kynoar（PVDF）With
0.15 kilogram of acetylene black mixed grinding is uniform, and 9 kilograms of N-Methyl pyrrolidones are added, and stirring forms uniform anode sizing agent.It should
Anode sizing agent is coated uniformly on 20 microns of aluminium foil, is then dried at 60 DEG C, punching, and a diameter of 1cm is made2Just
Working electrode is made by drying in polar circle piece.It is diaphragm that cathode, which uses amorphous carbon material, polypropylene screen, 1M LiPF 6/
(EC+DMC) (1:1) it is that electrolyte is assembled into battery.Constant current charge-discharge test is carried out to battery is made, voltage range is 2.5
Between ~ 4.6V, the discharge capacity for recording battery is as shown in table 1.
Table 1：
Claims (10)
1. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding, which is characterized in that specific preparation side
Method is：
（1）Using soluble nickel salt, cobalt salt, manganese salt, according to nickel, the molar ratio 1-x-y of cobalt, manganese:x:Y weighs the nickel salt, cobalt
Salt, manganese salt, and the nickel salt, cobalt salt, manganese salt are added in blender, high-speed stirred is uniformly mixed, obtains mixed powder,
In 0.5<1-x-y<1,0<X≤0.2,0<y≤0.2；
（2）The mixed powder is added in appropriate amount of deionized water, mixed solution is obtained, precipitation is added into the mixed solution
Agent after stirring evenly, adjusts pH=11-12, obtains nickelic ternary precursor lotion, persursor material is obtained by spray drying；
（3）The persursor material is placed in soaking and stirring in boiling water, gallium is added dropwise, until presoma surface is white
Jelly coats completely, obtains the presoma of gallium oxide package；
（4）Ball mill is added with the lithium source in the presoma that the gallium oxide is wrapped up, uniform by ball milling mixing, takes out powder
Body quickly heats up to 400-450 DEG C of heat preservation 2-5h, is warming up to calcines 4-5h at 700-720 DEG C later under oxygen-enriched environment,
After natural cooling, the nickelic ternary anode material of lithium battery of gallium oxide cladding is obtained.
2. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, the nickel salt is one kind in nickel chloride, nickelous carbonate, nickel nitrate, nickel sulfate, nickelous bromide, nickel fluoride, the cobalt salt
For one kind in cobalt chloride, cobalt carbonate, cobalt nitrate, cobaltous sulfate, cobalt acid sodium, cobaltous bromide, cobaltous fluoride, the manganese salt be manganese chloride,
One kind in manganese carbonate, manganese nitrate, manganese sulfate, manganous bromide, manganous fluoride.
3. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, the precipitating reagent is the mixed solution of sodium hydroxide and ammonium hydroxide, a concentration of 0.9-1.5mol/L of sodium hydroxide, ammonia
Water concentration is 2mol/L.
4. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, in the mixed solution, controls a concentration of 0.3-2.1mol/L of nickel salt.
5. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, the size of the persursor material is 8-40 microns.
6. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, control ball milling speed is 260-1200rpm, Ball-milling Time 30-50min.
7. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, step（3）The presoma of kind gallium oxide cladding, gallium oxide coating thickness are 0.08-0.20 μm.
8. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, step（4）Described in oxygen-enriched environment be oxygen content be 30-60%, and control carbon dioxide and other sour gas
The concentration of body is less than 0.09 ‰.
9. a kind of preparation method of the nickelic ternary anode material of lithium battery of gallium oxide cladding according to claim 1,
It is characterized in that, step（4）Described in the heating rate that quickly heats be 30-60 DEG C/min.
10. a kind of nickelic ternary anode material of lithium battery of gallium oxide cladding, which is characterized in that by any one of claim 1-9
The method is prepared.
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