CN109778301A - The preparation of one type monocrystalline lithium-rich oxide material and application - Google Patents
The preparation of one type monocrystalline lithium-rich oxide material and application Download PDFInfo
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Abstract
The preparation of one type monocrystalline lithium-rich oxide material and application, are related to lithium ion battery material technical field, and the positive electrode general formula is Li [Lix/(2+x)Mn2x/(2+x)M2(1‑x)/(2+x)]1‑βNβO2‑δWδ, wherein M=Mn1‑y‑zNiyCoz, at least one of N Ti, V, Cr, Al, La, B, Mo, Nb etc., at least one of W F, Cl, Br, S, P, I etc., 0.1≤y≤0.5,0≤z≤0.25,0.1≤x≤0.8,0≤β≤0.2,0≤δ≤0.2.There is lithium-rich manganese-based layered oxide positive electrode of the class monocrystalline pattern containing spinel structure in conjunction with what fused salt sintering method was prepared using co-precipitation, particle diameter is 1~10 μm, favorable dispersibility, size uniformity, and security performance is high, compacted density is high.
Description
Technical field
The present invention relates to lithium ion battery material technical fields, are to be related to a type monocrystalline lithium-rich more specifically
Oxide material, preparation method and application.
Background technique
With the rapid development of science and technology and the acceleration of process of industrialization, the mankind increase the consumption of the energy year by year, lead
Cause non-renewable fossil energy almost exhausted, problem of energy crisis is on the rise.It is well known that the burning of fossil energy can discharge
A large amount of exhaust gas and dust, cause serious environmental pollution.Therefore, develop green clean energy resource, preserve the ecological environment, implement can
Sustainable development strategy becomes the task of top priority in China.The green energy resources such as wind energy, solar energy, water energy, biological energy source should be opened extensively
Hair, and these electric energy can be converted to chemical energy as a kind of efficient energy storage device by lithium ion battery, so as in each neck
Domain is used.In recent years, the demand based on New-energy electric vehicle field to more high standard energy storage device, lithium ion battery is to height
The exploitation in the directions such as specific energy, high power density, high security, long circulation life, low cost is increasingly urgent.Positive electrode conduct
The important component of lithium ion battery directly determines the key property of lithium ion battery, therefore, exploitation high-performance, it is low at
This positive electrode is the key that promote energy-density lithium ion battery application.
The anode material for lithium-ion batteries developed at present mainly includes the cobalt acid lithium (LiCoO of stratiform2), lithium nickelate
(LiNiO2), LiMn2O4 (LiMnO2), spinel structure LiMn2O4 (LiMn2O4), olivine-type structure LiFePO4
(LiFePO4) and lithium nickel cobalt dioxide (LiNixCoyO2), nickle cobalt lithium manganate (LiNixCoyMnzO2) etc. layered oxides, specific volume
Amount is in 200mAhg-1Hereinafter, relative to stablizing in 350mAhg-1Positive electrode is low for above Carbon anode
Capacity has become the bottleneck for further increasing lithium ion battery energy density, needs the novel anode material of exploitation more height ratio capacity
Material.
Lithium-rich oxide anode material xLi2MnO3·(1-x)LiMO2(0 < x < 1, M are transition metal) has high ratio
Capacity (200~300mAhg-1) and high working voltage (> 4.5V), therefore it is with high energy density, and Mn element
The raising of content, while the content of Co element is reduced, the cost of material is reduced, and environmentally friendly.Therefore, rich lithium layer
Shape oxide anode material becomes the choosing for meeting the ideal of power vehicle lithium ion battery.Although lithium-rich oxide anode
Material has many advantages, but there is also some urgent problems to be solved: (1) the lithium-rich oxidation being widely studied at present
Object positive electrode is mostly the secondary spherical aggregate being made of primary particle, and with more fault of construction, and structure is not
Stablize, structure is easy to collapse in charge and discharge process；(2) had by the secondary spherical aggregate material that primary particle forms more
Gap, it is larger with electrolyte contacts area, will cause more side reaction；(3) secondary spherical aggregate structure fastness is poor,
Under higher pressure reality, it will cause secondary spherical aggregate and be crushed, side reaction increases, and then chemical property is caused to decline；(4) two
There are stress for the inside of secondary spherical agglomerates material, cause material easy to crack in cyclic process, so that the cycle performance of material
It is poor with thermal stability.
To solve the above problems, the present invention prepares bulky grain class monocrystalline lithium-rich oxide anode material, bulky grain class
Monocrystalline lithium-rich oxide anode material has the advantage that (1) higher compacting relative to secondary spherical aggregate material
Density, higher mechanical strength are non-breakable in electrode compacting process；(2) class monocrystal material specific surface area is relatively small, this
It has been reduced by the contact area of electrode material and electrolyte, to reduce the side reaction of electrode material and electrolyte, has improved electricity
The stable circulation performance and thermal stability of pole material；(3) class monocrystalline lithium-rich oxide anode material surface is more smooth, makes
It is simpler, uniform to obtain positive electrode surface cladding.(4) class monocrystal material also can be reduced Li+Crystal boundary is passed through during deintercalation
Number, to promote Li+Deintercalation speed, be conducive to improve electrode material high rate performance.
Furthermore in Spinel structure, empty tetrahedron and octahedron are coupled to each other by coplanar and total side, are formed three-dimensional
Lithium ion diffusion admittance, lithium ion can be made quickly to be embedded in and deviate from charge and discharge process, thus have good times
Rate performance.Meanwhile lithium-rich structure and spinel structure can be compatible with.If Spinel structure is introduced lithium-rich
Material structure stability not only can be improved in structure, while the high rate performance of material can be improved.
Chinese patent CN106920959A discloses " a kind of preparation method of monocrystalline richness lithium polynary positive pole material ", this method
Presoma is obtained by using carbonate co-precipitation, is then crushed presoma using ball grinding method, then under oxygen-enriched environment
It is sintered, technique is more complex, higher cost, and more importantly carbonate precursor hardness is lower, in ball mill grinding
Be readily formed small-sized and irregular fine particle, even if by later period sintering process in process parameter control be difficult
So that it is grown up, and fine particle be easy reunite, dispersibility it is very poor, these fine particles in electrochemical reaction process with electrolysis
Liquid contact, causes more side reaction, material electrochemical performance is caused to be decayed.
Chinese patent CN108557905A discloses " a kind of richness lithium material presoma and preparation method thereof, lithium-rich anode material
Material and preparation method thereof, lithium battery ", this method is by control synthesis " foliaceous " pattern richness lithium carbonate precursor as sintering
Starting material, control sintering process parameter obtains monocrystalline topology material, and H is added during the sintering process3BO3Or B2O3Additive is made
For fluxing agent, sintering temperature is reduced.It is well known that coprecipitation reaction process is very complicated, including precipitation reaction and complexing
Reaction, by carbonate concentration in control precipitating reagent, mixing salt solution concentration, ammonia concn, mixing velocity, mixing speed, anti-
Answer temperature and pH value condition etc., control synthesis little particle is spherical and " lamellar " carbonic acid salt precursor of primary fiber ordered stacks
Body is highly difficult, it is difficult to control, and the material morphology of patent acquisition, size are inhomogenous, this can seriously affect its cycle performance.
Summary of the invention
In order to overcome the above problem, the object of the present invention is to provide a kind of high capacity, low cost, high security, class list
Brilliant lithium-rich oxide anode material and preparation method thereof.This method has universality, process easily controllable, and is suitable for big
The characteristics of large-scale production.
Class monocrystalline lithium-rich oxide anode material prepared by the present invention, which is characterized in that contain micro spinelle
Structure, micro spinelle can further stabilizing material structure, and the quick diffusion admittance of lithium ion is provided, to improve class
Monocrystalline lithium-rich oxide anode material chemical property, makes it have higher charging and discharging capacity, stable cyclicity
It can be with good high rate performance.
To achieve the above object, according to one aspect of the present invention, a type monocrystalline is provided to aoxidize with lithium-rich
The preparation method of object positive electrode；
One type monocrystalline lithium-rich oxide anode material, general formula are Li [Lix/(2+x)Mn2x/(2+x)M2(1-x)/(2+x)]1-β
NβO2-δWδ, wherein M=Mn1-y-zNiyCoz, N Al, Si, Ca, Sc, Ti, V, Cr, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Ta,
At least one of La, Ir, W, Ce, Pr, Nd etc., at least one of W F, Cl, Br, S, P, I, 0.1≤y≤0.5,0≤z
≤ 0.25,0.1≤x≤0.8,0≤β≤0.2,0≤δ≤0.2, and contain spinel structure.To disperse single particle.
Class monocrystalline lithium-rich oxide further preferably described above has finishing coat or clad.It repairs on surface
Adorn layer or clad are as follows: one or more of compound of metallics, the metal be selected from Ti, Al, Co, V, Fe, Mn,
One or more of Ni, Zr, Ba, Nb, Mo or Sr etc., the compound are preferably oxide etc.；Nonmetalloid class
One or more of object or simple substance are closed, the nonmetalloid is selected from B, P, Si or C, the simple substance such as simple substance C, simple substance
Si etc., compound (such as Li of compound such as silica, P3PO4), compound (such as Li of B3BO3) etc..Or nonmetallic compound
Including NH4 +Salt compounds (such as ammonium fluoride), (such as CO (NH of organic matter containing N2)2), (such as C of organic matter containing C3H6N6) or containing C without
Machine object (such as CO2) one of or multiple combinations.
The purpose of the present invention can be realized by technical solution below:
A kind of preparation method containing spinel structure, class monocrystalline lithium-rich oxide anode material, including it is following
Several steps:
(1) ratio is measured by element chemistry, by the salt containing nickel metal ion, the salt containing cobalt metal ion, contains manganese gold
The salt for belonging to ion is dissolved in deionized water, obtains salting liquid a；Prepare sodium hydrate aqueous solution b；Prepare enveloping agent solution c；
(2) solution a, solution b and the solution c obtained step (1) is pumped into respectively under inert gas environment protection
In coprecipitation reaction kettle, and control temperature and time during coprecipitation reaction；
(3) " petal-shaped " can be obtained by sediment separation, washing and drying in the presoma for obtaining step (2)
Hydroxide precursor；
(4) by the compound of N dvielement described in the obtained presoma of step (3), Li source compound, structural formula
(preferred oxides), fused salt are fully ground mixing, are then placed into Muffle furnace, in 400~600 DEG C of range 3~6h of inside holding,
Temperature is raised to 700~900 DEG C again, keeps the temperature 1~10h, temperature is finally raised to 950~1200 DEG C, keeps the temperature 1~10h, it is cold with furnace
But to room temperature, then by obtained material disintegrating；
(5) the obtained material of step (4) is filtered, washing, vacuum drying.By the material after drying using heat treatment
Afterwards, of uniform size, favorable dispersibility class monocrystalline lithium-rich oxide anode material can be obtained.
It is further preferred:
Salt containing nickel metal ion described in step (1) is nickel sulfate, nickel acetate, nickel oxalate or nickel nitrate；It is described containing
The salt of cobalt metal ion is cobaltous sulfate, cobalt acetate, cobalt oxalate or cobalt nitrate；The salt containing manganese Metal ion be manganese sulfate,
Manganese acetate, manganese oxalate or manganese nitrate；
Sodium hydrate aqueous solution solubility described in step (1) is 1~6mol/L；The complexing agent is ammonia spirit, dense
Degree is 1~6mol/L；
Coprecipitation reaction process temperature described in step (2) is 20~70 DEG C, and the heating time is 1~10h, described anti-
Answering pH value is 9~12,400~1100rpm/min of mixing speed of the reaction kettle；
The size of the hydroxide precursor obtained described in step (3) is 1~10 μm；
Step (4) described Li source compound in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate or lithium nitrate one
Kind or multiple combinations；
Step (4) fused salt is selected from AxBy、AxCyOne or more of, wherein A is metal cation: Li+、Na+、
K+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+、Mo6+、Fe3+、La3+、Rb+, B F-、Cl-、Br-、I-、S2-, C CH3COO-、
OH-、 Wherein x be 1~6, and x be integer, y be 1~
6, and y is integer.In use, select the above components of molten salt one such or multiple combinations, the W according to contained in structural formula
Dvielement is selected；
Metal hydroxides presoma described in step (4), Li source compound are mixed according to the molar ratio of structural formula,
Metal hydroxides presoma carries out weighing with the molar ratio of fused salt for 1:1-10 and mixes；
Heat treatment temperature described in step (5) is 200~800 DEG C, and soaking time is 1~6h.
The class monocrystalline lithium-rich oxide anode material is having a size of 1~10 μm, it is preferable that optimum size is 2~6 μ
M, and component content of the spinel structure in entire material structure is 0~15%, and is not 0.
Preferably, the mole of any one in doped chemical N accounts for 0.01%~20%, W of Mn+M+N integral molar quantity
The mole of any one in doped chemical accounts for the 0.01%~10% of O+W integral molar quantity.
It is another aspect of this invention to provide that the present invention provides a kind of systems of surface modification class monocrystalline lithium-rich oxide
Preparation Method, it is characterised in that including the following:
The preparation method of the surface modification class monocrystalline lithium-rich oxide, including surface cladding and surface vapor are repaired
Decorations；
The preparation method of the surface cladding class monocrystalline lithium-rich oxide, using magnetic agitation method, chemical vapor deposition
One or more of area method, hydro-thermal method, sol-gal process.The covering material be metallics one of compound or
Several, the metal is selected from one or more of Ti, Al, Co, V, Fe, Mn, Ni, Zr, Ba, Nb, Mo or Sr etc., described
Compound is preferably oxide etc.；One or more of nonmetalloid class compound or simple substance, the nonmetalloid
Selected from B, P, Si or C, the simple substance such as simple substance C, simple substance Si etc., compound (such as Li of compound such as silica, P3PO4)、
Compound (such as Li of B3BO3) etc..Or nonmetallic compound includes NH4 +Salt compounds (such as ammonium fluoride), organic matter containing N
(such as CO (NH2)2), (such as C of organic matter containing C3H6N6) or (such as CO of inorganic matter containing C2) one of or multiple combinations.
The preparation method of the surface vapor modification class monocrystalline lithium-rich oxide, using solid sintering technology.It is described to repair
Exterior material is that nonmetallic compound includes NH4 +Salt compounds (such as ammonium fluoride), (such as CO (NH of organic matter containing N2)2), have containing C
Machine object (such as C3H6N6) or (such as CO of inorganic matter containing C2) one of or multiple combinations.
Advantages of the present invention:
(1) class monocrystalline lithium-rich oxide anode material provided by the invention, by the precipitating for regulating and controlling coprecipitation process
Naoh concentration, complexing agent ammonia concn, reaction temperature, reaction time, mixing speed and pH value condition etc. in agent, control are closed
At 1~10 μm of rich lithium hydroxide precursor, synthesized in conjunction with the method for fused salt sintering, the synthetic method have it is easy to operate,
It is environmentally protective and be suitable for large-scale production the features such as.
(2) presoma is synthesized by coprecipitation method, so that transition metal (nickel, cobalt, manganese etc.) Elemental redistribution is equal in product
It is even；By the way that fused salt is added, so that presoma and lithium salts in a melting environment, accelerate metal ion diffusion, make particle growth
The limitation for breaking presoma reunion afterwards to a certain extent, is dispersed into single particle, effectively prevents the group of particle during the growth process
It is poly-, be conducive to particle and equably grow up, obtains the bulky grain material of favorable dispersibility, size uniformity；The fused salt tool used simultaneously
There is the advantages of environmentally protective, to be easily recycled；Part fused salt also can be used as doped source and enter lithium-rich oxide anode material knot
In structure, to improve the chemical property of material.
(3) crush to the presoma before sintering the processing of ball milling compared with the existing technology, the present invention utilizes 1~10 μm
Rich lithium hydroxide precursor, in conjunction with fused salt sintering method synthesize, without carrying out crushing ball milling, therefore, can be avoided because
Fine powder or disintegrating slag are ground by transition when ball-milling treatment, this particle is difficult to remove in actual production and can be to positive electrode
Using the operation for leaving very big security risk, and grinding without crushing ball, this fine particle will not be generated.
(4) " lamellar " rich lithium material carbonate precursor compared with the existing technology, present invention only requires controls to synthesize ruler
Very little is 1~10 μm of rich lithium hydroxide precursor.Operation is simpler, easily controllable, it is easier to realize.
(5) the present invention provides a kind of bulk phase-doped and positive electrode surface and interface method of modifying easy to operate.
(6) raw material of the present invention is resourceful based on manganese element, and price is low, and small by market clout；This
The material is invented without or with a small amount of metallic cobalt, is had the advantages that environmental-friendly and low in cost.
(7) class monocrystalline lithium-rich oxide anode material prepared by the present invention contains micro spinel structure.It is micro
The introducing of spinelle can increase speed and the channel of lithium ion diffusion, can be improved the charge/discharge capacity and circulation of positive electrode
Performance.
In conclusion key parameter of the present invention by optimization hydroxide coprecipitation step, prepares having a size of 1~10 μm
The pattern with single crystal-like is prepared in rich lithium hydroxide precursor combination fused salt sintering, and particle diameter is 1~10 μm,
Favorable dispersibility, size uniformity also contain micro spinel structure on microcosmic, and security performance is high, compacted density is high
Lithium-rich anode material solves the problems, such as that lithium-rich anode material exists and aggregate second particle bring in practical applications
Defect improves the comprehensive electrochemical of lithium-rich anode material.Entire preparation process is simple, easily controllable, and single crystallization degree is high,
It is suitable for industrialized production.In addition, in conjunction with the bulk phase-doped electricity with the final acquisition of surface and interface modification with excellent electrochemical performance
Pole material.
Detailed description of the invention
Fig. 1 is the stereoscan photograph for the class monocrystalline lithium-rich oxide material that the embodiment of the present invention 1 provides；
Fig. 2 is the X ray diffracting spectrum for the class monocrystalline lithium-rich oxide material that the embodiment of the present invention 1 provides；
Fig. 3 be the embodiment of the present invention 1, embodiment 3, lithium ion battery provided by embodiment 6 first charge-discharge curve
Figure；
Fig. 4 is cycle performance curve graph of the lithium ion battery that provides of the embodiment of the present invention 1 at 1C
Specific embodiment
A specific embodiment of the invention is further described below in conjunction with attached drawing.
Embodiment 1:
By CoSO4·7H2O、NiSO4·6H2O and MnSO4·H2Stoichiometrically 1:3:8 is dissolved in deionized water O,
It is configured to the mixed metal ion sulfate liquor A of 2mol/L；NaOH is dissolved in deionized water, the molten of 4mol/L is configured to
Liquid B；Concentrated ammonia liquor is dissolved in deionized water, the solution C of 5mol/L is configured to；In an inert atmosphere by solution A, B and C
It is added in coprecipitation reaction kettle simultaneously with peristaltic pump, is 10.5 in pH value, temperature is 55 DEG C, under the conditions of revolving speed is 1000rpm
Stirring 3 hours；The solid product obtained after stirring is cleaned 8 times using deionized water, before subsequent vacuum drying obtains hydroxide
Drive body D；By presoma D, LiOHH21:1.6:4 is uniformly mixed O and KCl in molar ratio, is placed in corundum crucible and is forged
Burning processing, respectively in 500 DEG C, 800 DEG C, 1000 DEG C of calcinings 5h, 8h, 5h, heating rate is 3 DEG C/min.By sintered anode
Material disintegrating is cleaned 3 times, subsequent vacuum drying with deionized water.The sample after drying is again placed in Muffle furnace again later,
In 300 DEG C of roasting 3h, favorable dispersibility, larger-size class monocrystalline lithium-rich oxide anode is can be obtained in furnace cooling
Material.
Using the grain morphology and crystal structure of scanning electron microscope and the available embodiment 1 of X-ray diffraction, respectively
As depicted in figs. 1 and 2.The positive electrode prepared by the present embodiment it can be seen from the SEM figure of Fig. 1 has class monocrystalline pattern, divides
It is smooth to dissipate property good, size uniformity, surface.The embodiment 1 is prepared it can be seen from the refine result of the X diffraction pattern of Fig. 2
Lithium-rich anode material have micro spinelle, structural content 3.31%.
Obtained positive electrode and acetylene black and PTFE (aqueous solution) are mixed and rolled according to the ratio of 80:15:5 and is made
Then film is sliced and is compressed in aluminium net, be assembled into 2032 button cells and carry out electrochemical property test, performance map
As shown in Figure 3 and Figure 4.It can be found out by Fig. 3,4, the positive electrode first charge-discharge efficiency which is prepared is
71.2%, discharge capacity is higher, and cycle performance is good.
Comparative example 1:
By embodiment 1 obtained presoma D, LiOHH21:1.6 is uniformly mixed O in molar ratio, is placed in corundum earthenware
Calcination processing is carried out in crucible, respectively in 500 DEG C, 800 DEG C, 1000 DEG C of calcinings 5h, 8h, 5h, heating rate is 3 DEG C/min.It will burn
Positive electrode after knot crushes, and class monocrystalline lithium-rich anode material can be obtained.
The obtained lithium-rich oxide anode material well-formed of this comparative example, surface are smooth, but primary particle
Between agglomeration it is serious, bad dispersibility.
Embodiment 2:
By embodiment 1 obtained presoma D, LiOHH2O, 1:1.6:2:2 is uniformly mixed in molar ratio by NaCl, KCl,
It is placed in corundum crucible and carries out calcination processing, respectively in 500 DEG C, 800 DEG C, 1000 DEG C of calcinings 5h, 8h, 5h, heating rate 3
℃/min.Sintered positive electrode is crushed, is cleaned 3 times with deionized water, subsequent vacuum drying.It later again will be after drying
Sample is again placed in Muffle furnace, and in 300 DEG C of roasting 3h, class monocrystalline lithium-rich oxide anode is can be obtained in furnace cooling
Material.
Embodiment 3:
By embodiment 1 obtained presoma D, LiOHH2O、KCl、La2O31:1.6:4:0.01 is uniformly mixed in molar ratio
It closes, is placed in corundum crucible and carries out calcination processing, first in 600 DEG C of pre-burning 5h, heating rate is 5 DEG C/min, later 1000
DEG C calcining 10h, heating rate be 1 DEG C/min.Sintered positive electrode is crushed, is cleaned 3 times with deionized water, subsequent vacuum
Drying.The sample after drying is again placed in Muffle furnace again later, in 300 DEG C of roasting 3h, furnace cooling, can be obtained has
The class monocrystalline lithium-rich oxide anode material of La element doping.
Obtained positive electrode and acetylene black and PTFE (aqueous solution) are mixed and rolled according to the ratio of 80:15:5 and is made
Then film is sliced and is compressed in aluminium net, be assembled into 2032 button cells and carry out electrochemical property test, performance map
As shown in Figure 3.It can be found out by Fig. 3, the positive electrode first charge-discharge efficiency which is prepared is 76.3%, and
Discharge capacity is higher than undoped class monocrystalline positive electrode.
Embodiment 4:
By embodiment 1 obtained presoma D, LiOHH2O, KCl, LiF are uniform according to molar ratio 1:1.6:4:0.02
Mixing, is placed in corundum crucible and carries out calcination processing, respectively in 500 DEG C, 800 DEG C, 1000 DEG C of calcinings 5h, 8h, 5h, heating speed
Rate is 3 DEG C/min.Sintered positive electrode is crushed, is cleaned 3 times with deionized water, subsequent vacuum drying.It will dry again later
Sample after dry is again placed in Muffle furnace, and in 300 DEG C of roasting 3h, the class list with F element doping is can be obtained in furnace cooling
Brilliant lithium-rich oxide anode material.
Embodiment 5:
The positive electrode that isopropyl titanate, deionized water and embodiment 1 obtain is placed in ALD system respectively, at 200 DEG C
Under the conditions of carry out TiO2The surface ALD cladding.The device parameter for adjusting ALD, uses N2As purge gas.Repeat aforesaid operations
20 times, surface, which can be obtained, TiO2The class monocrystalline lithium-rich oxide anode material of cladding.
Embodiment 6:
By aluminium isopropoxide and the obtained class monocrystalline lithium-rich oxide anode material of embodiment 1 according to molar ratio
0.02:1 is weighed, and is dissolved in certain ethanol solution, is configured to mixed solution.Mixed solution is placed on magnetic stirring apparatus and is added
Heat, heating temperature are 100 DEG C, and the sample after being evaporated is dried in a vacuum drying oven.Sample after drying is placed in Muffle furnace
Middle carry out subsequent heat treatment, heat treatment temperature are 600 DEG C, heating time 5h.
Obtained positive electrode and acetylene black and PTFE (aqueous solution) are mixed and rolled according to the ratio of 80:15:5 and is made
Then film is sliced and is compressed in aluminium net, be assembled into 2032 button cells and carry out electrochemical property test, performance map
As shown in Figure 3.It can be found out by Fig. 3, compared with undoped class monocrystalline positive electrode, by surface A l2O3The positive material of cladding
Material charge/discharge capacity slightly reduces, but first charge-discharge efficiency significantly improves, and reaches 75.6%.
Embodiment 7:
By the obtained class monocrystalline lithium-rich oxide anode material of embodiment 1 and CO (NH2)2In molar ratio it is 1:
0.01 uniformly mixing, is put into corundum crucible, crucible is placed in tube furnace, be passed through argon gas, make full of argon gas in boiler tube, later
Close air inlet.300 DEG C are raised to the heating rate of 5 DEG C/min, keeps the temperature 3h.Sintered positive electrode deionized water is clear
It washes 2 times, subsequent vacuum drying.Sample after drying is again placed in Muffle furnace, in 300 DEG C of roasting 3h, cools to room with the furnace
The class monocrystalline lithium-rich oxide anode material by surface modification can be obtained in temperature.
The above is merely preferred embodiments of the present invention, it is not intended to limit the scope of the present invention.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (10)
1. a type monocrystalline lithium-rich oxide anode material, which is characterized in that general formula is Li [Lix/(2+x)Mn2x/(2+x)
M2(1-x)/(2+x)]1-βNβO2-δWδ, wherein M=Mn1-y-zNiyCoz, N Al, Si, Ca, Sc, Ti, V, Cr, Cu, Zn, Sr, Y, Zr,
At least one of Nb, Mo, Ru, Ta, La, Ir, W, Ce, Pr, Nd etc., at least one of W F, Cl, Br, S, P, I, 0.1≤
Y≤0.5,0≤z≤0.25,0.1≤x≤0.8,0≤β≤0.2,0≤δ≤0.2, and contain spinel structure.
2. type monocrystalline lithium-rich oxide anode material described in accordance with the claim 1, which is characterized in that the class list
Brilliant lithium-rich oxide anode material is having a size of 1~10 μm, it is preferable that optimum size is 2~6 μm.
3. type monocrystalline lithium-rich oxide anode material described in accordance with the claim 1, which is characterized in that spinelle knot
Component content of the structure in entire material structure is 0~15%, and is not 0.
4. according to the described in any item type monocrystalline lithium-rich oxide anode materials of claim 1-3, which is characterized in that
The class monocrystalline lithium-rich oxide has finishing coat or clad；Finishing coat or clad are as follows: metal object
One or more of compound of matter, the metal are selected from Ti, Al, Co, V, Fe, Mn, Ni, Zr, Ba, Nb, Mo or Sr etc.
One or more of, the compound is preferably oxide；It or is one of nonmetalloid class compound or simple substance
Or it is several, the nonmetalloid is selected from B, P, Si or C or nonmetallic compound includes NH4 +Salt compounds, have containing N
One of machine object, organic matter containing C or inorganic matter containing C or multiple combinations.
5. the method for preparing the described in any item type monocrystalline lithium-rich oxide anode materials of claim 1-4, special
Sign is, comprising the following steps:
(1) by element chemistry measure ratio, by the salt containing nickel metal ion, the salt containing cobalt metal ion, containing manganese Metal from
The salt of son is dissolved in deionized water, obtains salting liquid a；Prepare sodium hydrate aqueous solution b；Prepare enveloping agent solution c；
(2) solution a, solution b and the solution c obtained step (1) is pumped into coprecipitated respectively under inert gas environment protection
In the reaction kettle of shallow lake, and control temperature and time during coprecipitation reaction；
(3) hydrogen-oxygen of " petal-shaped " can be obtained by sediment separation, washing and drying in the presoma for obtaining step (2)
Compound presoma；
(4) (preferably by the compound of N dvielement described in the obtained presoma of step (3), Li source compound, structural formula
Oxide), fused salt be fully ground mixing, be then placed into Muffle furnace, in 400~600 DEG C of range 3~6h of inside holding, then will
Temperature is raised to 700~900 DEG C, keeps the temperature 1~10h, and temperature is finally raised to 950~1200 DEG C, keeps the temperature 1~10h, cools to the furnace
Room temperature, then by obtained material disintegrating；
(5) the obtained material of step (4) is filtered, washing, vacuum drying；By the material after drying using heat treatment after,
Of uniform size, favorable dispersibility class monocrystalline lithium-rich oxide anode material can be obtained.
6. according to the method for claim 5, which is characterized in that the salt containing nickel metal ion described in step (1) is sulfuric acid
Nickel, nickel acetate, nickel oxalate or nickel nitrate；The salt containing cobalt metal ion is cobaltous sulfate, cobalt acetate, cobalt oxalate or nitric acid
Cobalt；The salt containing manganese Metal ion is manganese sulfate, manganese acetate, manganese oxalate or manganese nitrate；Sodium hydroxide described in step (1)
Aqueous solution solubility is 1~6mol/L；The complexing agent is ammonia spirit, and concentration is 1~6mol/L；Step (4) described lithium source
Compound is selected from one of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate or lithium nitrate or multiple combinations；Step (4) is described
Fused salt is selected from AxBy、AxCyOne or more of, wherein A is metal cation: Li+、Na+、K+、Cs+、Mg2+、Ca2+、Sr2+、
Ba2+、Al3+、Mo6+、Fe3+、La3+、Rb+, B F-、Cl-、Br-、I-、S2-, C CH3COO-、OH-、Wherein x is 1~6, and x is integer, and y is 1~6,
And y is integer；In use, select the above components of molten salt one such or multiple combinations, the member of the W class according to contained in structural formula
Element is selected；Coprecipitation reaction process temperature described in step (2) is 20~70 DEG C, and the heating time is 1~10h, institute
Stating pH value in reaction is 9~12,400~1100rpm/min of mixing speed of the reaction kettle；The hydrogen obtained described in step (3)
The size of oxide precursor is 1~10 μm.
7. according to the method for claim 5, which is characterized in that metal hydroxides presoma, lithium source described in step (4)
Compound is mixed according to the molar ratio of structural formula, and the molar ratio of metal hydroxides presoma and fused salt is 1:1-10 progress
Weigh mixing；Heat treatment temperature described in step (5) is 200~800 DEG C, and soaking time is 1~6h.
8. according to the method for claim 5, which is characterized in that the mole of any one in doped chemical N accounts for Mn+M+
The mole of any one in 0.01%~20%, the W doped chemical of N integral molar quantity account for O+W integral molar quantity 0.01%~
10%.
9. according to the method for claim 5, which is characterized in that the class monocrystalline lithium-rich oxide is repaired with surface
Adorn the preparation method of layer or clad, including surface cladding and surface vapor modification；
The preparation method of surface cladding class monocrystalline lithium-rich oxide, using magnetic agitation method, chemical vapour deposition technique,
One or more of hydro-thermal method, sol-gal process；The covering material is one or more of the compound of metallics,
The metal is selected from one or more of Ti, Al, Co, V, Fe, Mn, Ni, Zr, Ba, Nb, Mo or Sr, the compound
Preferably oxide etc.；One or more of nonmetalloid class compound or simple substance, the nonmetalloid be selected from B,
P, Si or C, the level of cladding are single-layer or multi-layer；
The preparation method of the surface vapor modification class monocrystalline lithium-rich oxide, using solid sintering technology；The modification material
Material is that nonmetallic compound includes NH4 +One of salt compounds, organic matter containing N, organic matter containing C or inorganic matter containing C or
Multiple combinations.
10. a kind of battery, which is characterized in that include the described in any item type monocrystalline lithium-rich oxidations of claim 1-4
Object positive electrode.
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