CN110504432A - Nickle cobalt lithium manganate composite material and preparation method, lithium battery anode and preparation method thereof, lithium battery and power supply unit - Google Patents
Nickle cobalt lithium manganate composite material and preparation method, lithium battery anode and preparation method thereof, lithium battery and power supply unit Download PDFInfo
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- CN110504432A CN110504432A CN201910807848.8A CN201910807848A CN110504432A CN 110504432 A CN110504432 A CN 110504432A CN 201910807848 A CN201910807848 A CN 201910807848A CN 110504432 A CN110504432 A CN 110504432A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention provides a kind of nickle cobalt lithium manganate composite material and preparation method, lithium battery anode and preparation method thereof, lithium battery and power supply unit.The preparation method of nickle cobalt lithium manganate composite material: nickle cobalt lithium manganate precursor, lithium source, doped compound are mixed, first time roasting is then carried out；The product of first time roasting is mixed with cladding compound, second is carried out and roasts；Nickle cobalt lithium manganate precursor includes the first presoma and the second presoma, and the first presoma is Ni1/3Co1/3Mn1/3(OH)2, the second presoma includes Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2One of or it is a variety of.The preparation method of nickle cobalt lithium manganate composite material provided by the present application, improves multiplying power, circulation, storage and the power-performance of ternary material, and structure and thermal stability are good.
Description
Technical field
The present invention relates to Material Field more particularly to a kind of nickle cobalt lithium manganate composite material and preparation methods, lithium battery
Anode and preparation method thereof, lithium battery and power supply unit.
Background technique
Continuous attention with the fast development and people of global economy to environmental problem, new-energy automobile are increasingly subject to city
Field favor.Anode material for lithium-ion batteries is material the most key in battery, lithium ion cell positive material currently on the market
Material mainly has cobalt acid lithium, LiMn2O4, LiFePO 4 and nickle cobalt lithium manganate (ternary material).
Nickle cobalt lithium manganate uses relatively inexpensive nickel and manganese instead of cobalt a large amount of in cobalt acid lithium, thus in terms of its cost
Advantage is clearly.Meanwhile compared with other anode material for lithium-ion batteries, big, stable structure, safety with reversible capacity
The advantage that energy is good, conductivity is high and thermal stability is good, nickel-cobalt lithium manganate material have very big market prospects.
The LiNi more early developed1/3Co1/3Mn1/3O2The capacity of material is lower, and cobalt content is high, expensive and toxic,
Limit its large-scale application.
In view of this, special propose the application.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of nickle cobalt lithium manganate composite material, preparation process letter
It is single, improve multiplying power, circulation, storage and the power-performance of ternary material.
The second object of the present invention is to provide a kind of nickle cobalt lithium manganate composite material, and capacity is high, has extended cycle life, cost
Low, structural stability and thermal stability are high.
The third object of the present invention is to provide a kind of lithium battery anode, uses the nickle cobalt lithium manganate composite material system
.
The fourth object of the present invention is to provide a kind of preparation method of lithium battery anode, simple process.
The fifth object of the present invention is to provide a kind of lithium battery, including the lithium battery anode.
The sixth object of the present invention is to provide a kind of power supply unit, including the lithium battery.
In order to achieve the above object, the present invention the following technical scheme is adopted:
A kind of preparation method of nickle cobalt lithium manganate composite material, comprising:
Nickle cobalt lithium manganate precursor, lithium source, doped compound are mixed to get the first mixture, then carry out first time roasting
It burns；
The product of first time roasting and cladding compound are mixed to get the second mixture, second is carried out and roasts, obtain
Nickle cobalt lithium manganate composite material；
The nickle cobalt lithium manganate precursor includes the first presoma and the second presoma, and first presoma is Ni1/ 3Co1/3Mn1/3(OH)2, second presoma includes Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2With
Ni0.8Co0.1Mn0.1(OH)2One of or it is a variety of.
Concentration gradient material is more readily formed in lithiumation sintering after the mixing of two class presomas, for improving the overall performance of battery core
There is great role.First presoma and the second presoma are layer structure, its layer structure remains unchanged after the two mixing, and
And the chemical property of the two is complementary, solves the problems, such as that specific capacity is low, cobalt content is high, at high cost, and be used in mixed way rear whole
The cycle performance of body is not decayed significantly, and cycle performance is maintained.
The doped metallic elements in ternary material lattice not only can be improved electronic conductivity and ionic conductivity, may be used also
To improve the output power of battery, the stability (especially thermal stability) of ternary material is improved.Reason is mainly non-equivalence sun
Ion doping leads to the raising of ternary material transition metal ions valence state, and perhaps reduction generates hole or electronics, changes material
Band structure, to improve its native electronic conductivity；The cation of doping enters material of main part lattice, reduces cation
Mixing degree, it is suppressed that the precipitation of oxygen reduces the electrode polarization in electrochemical reaction process, improves electrochemistry cycle performance,
And structure and thermal stability.
In ternary material surface clad element, Li-M-O chemical combination is formed on ternary material surface by high-temperature heat treatment
Object can resist corrosion of the HF for active material, reduce surface impedance and improve cyclical stability；In addition it also will form M-O-
F and/or M-F compound can become the cleaning agent of HF acid, limit the content of HF acid in electrolyte.Its result is exactly element packet
Cover the reversible specific capacity that can improve material, cycle performance, high rate performance, thermal stability and storage performance.
Preferably, the mass ratio of first presoma and second presoma is (3-6): (1-2).
Preferably, the lithium source includes one in carbonate, hydroxide, oxide, acetate and the peroxide of lithium
Kind is a variety of.
Preferably, the doped compound includes oxide and hydroxide, the oxide of Ti and hydroxide, Zr of Mg
Oxide and one of hydroxide, the oxide of Al and hydroxide or a variety of.
Preferably, the cladding compound includes oxide and hydroxide, the oxide of Ti and hydroxide, Zr of Zn
Oxide and the mixing of one or more of hydroxide, the oxide of Al and hydroxide.
To the proportion of presoma, lithium source, doped compound, the preferred of compound is coated, it can be preferably to ternary material
Performance improved, obtain more excellent performance of nickle cobalt lithium manganate composite material.
It preferably, further include cosolvent in first mixture, the cosolvent includes the oxidation of the oxide of B, Ba
One of object, the oxide of Bi, the oxide of Li, the oxide of K, the oxide of Na, the oxide of Ca and oxide of Mg
Or it is a variety of.
The use of cosolvent facilitates the progress of doping, promotes doping effect.
Preferably, further include grain refiner in second mixture, the grain refiner include Ti oxide,
One of oxide of the oxide of Nb, the oxide of V and Al is a variety of.
The use of grain refiner facilitates the progress of cladding.
Preferably, the temperature of the first time roasting is 700-1000 DEG C, soaking time 10-20h；Second of roasting
The temperature of burning is 650-800 DEG C, soaking time 8-15h.
Optionally, the temperature of the first time roasting can be between 700,800,900,1000 and 700-1000 DEG C
Any value, soaking time can any values between 10h, 12h, 15h, 17h, 19h, 20h and 10-20h；Described second
The temperature of roasting can be any value between 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C and 650-800 DEG C, and soaking time can be with
Any value between 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and 8-15h.
Preferably, the molar ratio of the nickle cobalt lithium manganate precursor, the doped compound and the cladding compound is
(0.990-0.992): (0.001-0.004): (0.005-0.007), the doped compound and the molar ratio of the lithium source are
0.02-0.05:1.
Control for usage ratio can obtain preferably doping and covered effect.
Optionally, first mixture and second mixture are all made of high energy batch mixer and are mixed to get.
It is blended by high energy batch mixer, more uniformly, effect is more preferable for mixing, for improving the stabilization of later period slurrying
Property, reduce dispersion difficulty, improve battery core consistency, have a significant effect.
A kind of nickle cobalt lithium manganate composite material is made using the preparation method of the nickle cobalt lithium manganate composite material.
A kind of lithium battery anode is made using the nickle cobalt lithium manganate composite material.
A kind of preparation method of the lithium battery anode, comprising:
The nickle cobalt lithium manganate composite material, conductive agent, binder and solvent are mixed to get slurry, then by the slurry
Material is coated on substrate, and drying obtains the lithium battery anode.
Preferably, the nickle cobalt lithium manganate composite material, the conductive agent, the binder mass ratio be (94-97):
(1.5-3): (1.5-3)；The solid content of the slurry is 50-70wt%.
Preferably, the conductive agent includes conductive carbon black, and the binder includes Kynoar, and the solvent includes N-
Methyl pyrrolidone, the substrate include aluminium foil.
Optionally, the single side surface density of the lithium battery anode is 100-200mg/cm2, compacted density 3.1-3.3g/
cm3。
Optionally, the single side surface density of the lithium battery anode can be 100mg/cm2、110mg/cm2、120mg/cm2、
130mg/cm2、140mg/cm2、150mg/cm2、160mg/cm2、170mg/cm2、180mg/cm2、190mg/cm2、200mg/cm2
And 150-200mg/cm2Between any value, compacted density can be 3.1g/cm3、3.2g/cm3、3.3g/cm3And 3.1-
3.3g/cm3Between any value.
A kind of lithium battery, including the lithium battery anode.
A kind of power supply unit, including the lithium battery.
Compared with prior art, beneficial effects of the present invention include at least:
Select the nickle cobalt lithium manganate precursor of two kinds of chemical property complementations as raw material, the second presoma compensates for first
The defect that presoma specific capacity is low, cobalt content is high, price is high, and material can be improved with part the first forerunner bluk recombination
Capacity, and cycle performance is enabled to keep normal.Concentration gradient is more readily formed in lithiumation sintering after two kinds of presoma mixing
Material, the overall performance for improving battery core have great role.Doped compound improves the high rate performance of ternary material, improves
Power-performance；Cladding compound improves the cycle performance and storage performance of ternary material；Element doping and cladding improve
The structural stability and thermal stability of material.
Specific embodiment
Term as used herein:
" by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing "
Or its any other deformation, it is intended that cover non-exclusionism includes.For example, composition, step, method comprising listed elements,
Product or device are not necessarily limited to those elements, but may include not expressly listed other elements or such composition, step
Suddenly, method, product or the intrinsic element of device.
Conjunction " by ... form " exclude any element that do not point out, step or component.If in claim,
This phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
In these embodiments, unless otherwise specified, described part and percentage is by mass.
" mass parts " refer to the basic measurement unit for indicating the mass ratio relationship of multiple components, and 1 part can indicate arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of component A are a parts, the matter of B component
Measuring part is b parts, then it represents that the quality of component A and the mass ratio a:b of B component.Alternatively, indicating that the quality of component A is aK, B group
The quality divided is bK (K is arbitrary number, indicates multiplying factor).It can not misread, unlike mass fraction, all components
The sum of mass parts be not limited to 100 parts of limitation.
"and/or" is used to indicate that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B).
Embodiment of the present invention is described in detail below in conjunction with specific embodiment, but those skilled in the art
It will be understood that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.It is not specified in embodiment
Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer,
It is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.2Mn0.3(OH)2It is body before 3:1 composition nickle cobalt lithium manganate according to mass ratio
Body, with Li2CO3For lithium source, add doped compound Zr (OH)4、Mg(OH)2, and cosolvent MgO is added, it is added to high speed grinding
In machine after it is sufficiently mixed, in 900 DEG C of Muffle kiln roasting 12h；
Addition cladding compound Ti (OH) into the product of roasting4, and grain refiner TiO is added2, it is added to high speed and grinds
Continue stirring in grinding machine after it is sufficiently mixed, in 800 DEG C of Muffle kiln roasting 10h, obtains nickle cobalt lithium manganate composite material.
Wherein, the molar ratio of nickle cobalt lithium manganate precursor, doped chemical and cladding element is 0.992:0.002:0.006.
It is with gained nickle cobalt lithium manganate composite material, Super-P (conductive carbon black) and binder PVDF (Kynoar)
Raw material is dissolved in NMP (N-Methyl pyrrolidone) stirring according to the mixing of 94%:3%:3% mass ratio and prepares slurry, controls slurry
Solid content be 50wt%, anode sizing agent is spread evenly across on the aluminium foil of 16 μ m thicks, and then dry, roll-in and cross cutting；It is negative
Pole using graphite, conductive agent and binder as raw material is mixed in deionized water according to 95%:2%:3% mass ratio and prepares slurry,
Slurry is coated on 8 μ m-thick copper foils, and then drying, roll-in and cross cutting；Control positive and negative anodes pole piece cut-parts width is than 0.98, positive and negative anodes
Pole piece length ratio is 0.97, is assembled into soft bag lithium ionic cell.It prepares in cell process, controlling anode coating single side surface density is
100mg/cm2, it is 54mg/cm that cathode, which is coated with single side surface density,2；Anode pole piece compacted density is 3.2g/cm3, cathode pole piece compacting
Density 1.35g/cm3。
To above-mentioned soft bag lithium ionic cell sample test gram volume and normal-temperature circulating performance data.Gram volume is according to as follows
Test carries out: carrying out constant-current charge to 4.2V to battery using 1C rate, 4.2V constant-voltage charge, cut-off current is that (C is electricity to 0.05C
The nominal capacity in pond)；Then it is discharged again with 1C rate, is discharged to 3.0V；In triplicate, average value is as capability value；Gram
Capacity is the capacity of performance divided by the quality of active materials all in battery core.Normal temperature circulation is carried out according to following test: using 1C
Rate carries out constant-current charge to 4.2V to battery, and 4.2V constant-voltage charge, cut-off current is 0.05C (nominal capacity that C is battery)；So
It is discharged again with 1C rate afterwards, is discharged to 3.0V, repeat the process, until residual capacity is the 80% of initial capacity.
Embodiment 2
Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.2Mn0.3(OH)2It is body before 4:1 composition nickle cobalt lithium manganate according to mass ratio
Body, with Li2CO3For lithium source, add doped compound Zr (OH)4、Al(OH)3, and cosolvent MgO, B is added2O3, it is added to high speed
In grinder after it is sufficiently mixed, in 880 DEG C of Muffle kiln roasting 15h；
Addition cladding compound Zn (OH) into the product of roasting2, and grain refiner TiO is added2, it is added to high speed and grinds
Continue stirring in grinding machine after it is sufficiently mixed, in 720 DEG C of Muffle kiln roasting 13h, obtains nickle cobalt lithium manganate composite material.
Wherein, the molar ratio of nickle cobalt lithium manganate precursor, doped chemical and cladding element is 0.992:0.002:0.006.
It is with gained nickle cobalt lithium manganate composite material, Super-P (conductive carbon black) and binder PVDF (Kynoar)
Raw material is dissolved in NMP (N-Methyl pyrrolidone) stirring according to the mixing of 97%:1.5%:1.5% mass ratio and prepares slurry, controls
The solid content of slurry is 70wt%, anode sizing agent is spread evenly across on the aluminium foil of 16 μ m thicks, and then drying, roll-in and mould
It cuts；Cathode is mixed in deionized water according to 95%:2%:3% mass ratio as raw material using graphite, conductive agent and binder and prepares
Slurry, slurry are coated on 8 μ m-thick copper foils, and then drying, roll-in and cross cutting；Control positive and negative anodes pole piece cut-parts width than 0.98,
Positive and negative anodes pole piece length ratio is 0.97, is assembled into soft bag lithium ionic cell.It prepares in cell process, controls anode coating single side face
Density is 200mg/cm2, it is 54mg/cm that cathode, which is coated with single side surface density,2；Anode pole piece compacted density is 3.1g/cm3, cathode pole
Piece compacted density 1.35g/cm3。
Test method is the same as embodiment 1.
Embodiment 3
Ni1/3Co1/3Mn1/3(OH)2、Ni0.6Co0.2Mn0.2(OH)2It is body before 3:1 composition nickle cobalt lithium manganate according to mass ratio
Body, with Li2CO3For lithium source, add doped compound Zr (OH)4、Mg(OH)2, and cosolvent MgO is added, it is added to high speed grinding
In machine after it is sufficiently mixed, in 880 DEG C of Muffle kiln roasting 12h；
Addition cladding compound Ti (OH) into the product of roasting4, and grain refiner TiO is added2, it is added to high speed and grinds
Continue stirring in grinding machine after it is sufficiently mixed, in 800 DEG C of Muffle kiln roasting 10h, obtains nickle cobalt lithium manganate composite material.
Wherein, the molar ratio of nickle cobalt lithium manganate precursor, doped chemical and cladding element is 0.991:0.003:0.006.
It is with gained nickle cobalt lithium manganate composite material, Super-P (conductive carbon black) and binder PVDF (Kynoar)
Raw material is dissolved in NMP (N-Methyl pyrrolidone) stirring according to the mixing of 94%:3%:3% mass ratio and prepares slurry, controls slurry
Solid content be 70wt%, anode sizing agent is spread evenly across on the aluminium foil of 16 μ m thicks, and then dry, roll-in and cross cutting；It is negative
Pole using graphite, conductive agent and binder as raw material is mixed in deionized water according to 95%:2%:3% mass ratio and prepares slurry,
Slurry is coated on 8 μ m-thick copper foils, and then drying, roll-in and cross cutting；Control positive and negative anodes pole piece cut-parts width is than 0.98, positive and negative anodes
Pole piece length ratio is 0.97, is assembled into soft bag lithium ionic cell.It prepares in cell process, controlling anode coating single side surface density is
150mg/cm2, it is 54mg/cm that cathode, which is coated with single side surface density,2；Anode pole piece compacted density is 3.1g/cm3, cathode pole piece compacting
Density 1.35g/cm3。
Test method is the same as embodiment 1.
Embodiment 4
Ni1/3Co1/3Mn1/3(OH)2、Ni0.6Co0.2Mn0.2(OH)2It is body before 4:1 composition nickle cobalt lithium manganate according to mass ratio
Body, with Li2CO3For lithium source, add doped compound Zr (OH)4、Al(OH)3, and cosolvent MgO, B is added2O3, it is added to high speed
In grinder after it is sufficiently mixed, in 850 DEG C of Muffle kiln roasting 15h；
Addition cladding compound Zn (OH) into the product of roasting2, and grain refiner TiO is added2, it is added to high speed and grinds
Continue stirring in grinding machine after it is sufficiently mixed, in 720 DEG C of Muffle kiln roasting 13h, obtains nickle cobalt lithium manganate composite material.
Wherein, the molar ratio of nickle cobalt lithium manganate precursor, doped chemical and cladding element is 0.991:0.003:0.006.
It is with gained nickle cobalt lithium manganate composite material, Super-P (conductive carbon black) and binder PVDF (Kynoar)
Raw material is dissolved in NMP (N-Methyl pyrrolidone) stirring according to the mixing of 96%:2%:2% mass ratio and prepares slurry, controls slurry
Solid content be 60wt%, anode sizing agent is spread evenly across on the aluminium foil of 16 μ m thicks, and then dry, roll-in and cross cutting；It is negative
Pole using graphite, conductive agent and binder as raw material is mixed in deionized water according to 95%:2%:3% mass ratio and prepares slurry,
Slurry is coated on 8 μ m-thick copper foils, and then drying, roll-in and cross cutting；Control positive and negative anodes pole piece cut-parts width is than 0.98, positive and negative anodes
Pole piece length ratio is 0.97, is assembled into soft bag lithium ionic cell.It prepares in cell process, controlling anode coating single side surface density is
180mg/cm2, it is 54mg/cm that cathode, which is coated with single side surface density,2；Anode pole piece compacted density is 3.1g/cm3, cathode pole piece compacting
Density 1.35g/cm3。
Test method is the same as embodiment 1.
Embodiment 5
Ni1/3Co1/3Mn1/3(OH)2、Ni0.8Co0.1Mn0.1(OH)2It is body before 3:1 composition nickle cobalt lithium manganate according to mass ratio
Body, with Li2CO3For lithium source, add doped compound Zr (OH)4、Mg(OH)2, and cosolvent MgO is added, it is added to high speed grinding
In machine after it is sufficiently mixed, in 850 DEG C of Muffle kiln roasting 12h；
Addition cladding compound Ti (OH) into the product of roasting4, and grain refiner TiO is added2, it is added to high speed and grinds
Continue stirring in grinding machine after it is sufficiently mixed, in 750 DEG C of Muffle kiln roasting 10h, obtains nickle cobalt lithium manganate composite material.
Wherein, the molar ratio of nickle cobalt lithium manganate precursor, doped chemical and cladding element is 0.990:0.004:0.006.
It is with gained nickle cobalt lithium manganate composite material, Super-P (conductive carbon black) and binder PVDF (Kynoar)
Raw material is dissolved in NMP (N-Methyl pyrrolidone) stirring according to the mixing of 94%:3%:3% mass ratio and prepares slurry, controls slurry
Solid content be 70wt%, anode sizing agent is spread evenly across on the aluminium foil of 16 μ m thicks, and then dry, roll-in and cross cutting；It is negative
Pole using graphite, conductive agent and binder as raw material is mixed in deionized water according to 95%:2%:3% mass ratio and prepares slurry,
Slurry is coated on 8 μ m-thick copper foils, and then drying, roll-in and cross cutting；Control positive and negative anodes pole piece cut-parts width is than 0.98, positive and negative anodes
Pole piece length ratio is 0.97, is assembled into soft bag lithium ionic cell.It prepares in cell process, controlling anode coating single side surface density is
160mg/cm2, it is 54mg/cm that cathode, which is coated with single side surface density,2；Anode pole piece compacted density is 3.2g/cm3, cathode pole piece compacting
Density 1.35g/cm3。
Test method is the same as embodiment 1.
Embodiment 6
Ni1/3Co1/3Mn1/3(OH)2、Ni0.8Co0.1Mn0.1(OH)2It is body before 4:1 composition nickle cobalt lithium manganate according to mass ratio
Body, with Li2CO3For lithium source, add doped compound Zr (OH)4、Al(OH)3, and cosolvent MgO, B is added2O3, it is added to high speed
In grinder after it is sufficiently mixed, in 800 DEG C of Muffle kiln roasting 15h；
Addition cladding compound Zn (OH) into the product of roasting2, and grain refiner TiO is added2, it is added to high speed and grinds
Continue stirring in grinding machine after it is sufficiently mixed, in 700 DEG C of Muffle kiln roasting 13h, obtains nickle cobalt lithium manganate composite material.
Wherein, the molar ratio of nickle cobalt lithium manganate precursor, doped chemical and cladding element is 0.990:0.004:0.006.
It is with gained nickle cobalt lithium manganate composite material, Super-P (conductive carbon black) and binder PVDF (Kynoar)
Raw material is dissolved in NMP (N-Methyl pyrrolidone) stirring according to the mixing of 96%:2%:2% mass ratio and prepares slurry, controls slurry
Solid content be 60wt%, anode sizing agent is spread evenly across on the aluminium foil of 16 μ m thicks, and then dry, roll-in and cross cutting；It is negative
Pole using graphite, conductive agent and binder as raw material is mixed in deionized water according to 95%:2%:3% mass ratio and prepares slurry,
Slurry is coated on 8 μ m-thick copper foils, and then drying, roll-in and cross cutting；Control positive and negative anodes pole piece cut-parts width is than 0.98, positive and negative anodes
Pole piece length ratio is 0.97, is assembled into soft bag lithium ionic cell.It prepares in cell process, controlling anode coating single side surface density is
120mg/cm2, it is 54mg/cm that cathode, which is coated with single side surface density,2；Anode pole piece compacted density is 3.3g/cm3, cathode pole piece compacting
Density 1.35g/cm3。
Test method is the same as embodiment 1.
Comparative example 1
Difference from Example 1 is, Ni is only used only1/3Co1/3Mn1/3(OH)2As presoma.
Comparative example 2
Difference from Example 2 is, Ni is only used only1/3Co1/3Mn1/3(OH)2As presoma.
Comparative example 3
Difference from Example 3 is, Ni is only used only1/3Co1/3Mn1/3(OH)2As presoma.
Comparative example 4
Difference from Example 4 is, Ni is only used only1/3Co1/3Mn1/3(OH)2As presoma.
Comparative example 5
Difference from Example 5 is, Ni is only used only1/3Co1/3Mn1/3(OH)2As presoma.
Comparative example 6
Difference from Example 6 is, Ni is only used only1/3Co1/3Mn1/3(OH)2As presoma.
The embodiment 1-6 and comparative example 1-6 lithium battery prepared is tested for the property, performance is as shown in the table:
1 the performance test results of table
As seen from the above table, embodiment 1 compares comparative example 1, and gram volume, which plays, increases by 5.0%, and cycle performance does not obviously decline
Subtract；Embodiment 2 compares comparative example 2, and gram volume, which plays, increases by 5.5%, and cycle performance is not obviously decayed；Embodiment 3 compared to pair
Ratio 3, gram volume, which plays, increases by 7.0%, and cycle performance is not obviously decayed；Embodiment 4 compares comparative example 4, and gram volume plays
Increase by 7.5%, cycle performance is not obviously decayed；Embodiment 5 compares comparative example 5, and gram volume, which plays, increases by 10.0%, cyclicity
Can obviously it not decay；Embodiment 6 compares comparative example 6, and gram volume, which plays, increases by 11.0%, and cycle performance is not obviously decayed.
The application improves ternary material by the compound, preferably of nickle cobalt lithium manganate precursor, and by doping and cladding
Properties, obtain the nickle cobalt lithium manganate composite material that at low cost, capacity is big, cycle performance is maintained.
Using electrode made from nickle cobalt lithium manganate composite material provided by the present application, then manufactured battery, can be used for
It directly powers, can be used for being fabricated to power supply unit and be powered.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
In addition, it will be appreciated by those of skill in the art that although some embodiments in this include institute in other embodiments
Including certain features rather than other feature, but the combination of the feature of different embodiment means in the scope of the present invention
Within and form different embodiments.For example, in claims above, embodiment claimed it is any it
One can in any combination mode come using.The information disclosed in the background technology section is intended only to deepen to the present invention
General background technology understanding, and be not construed as recognizing or imply that information composition has been this field skill in any form
The prior art well known to art personnel.
Claims (14)
1. a kind of preparation method of nickle cobalt lithium manganate composite material characterized by comprising
Nickle cobalt lithium manganate precursor, lithium source, doped compound are mixed to get the first mixture, then carry out first time roasting；
The product of first time roasting and cladding compound are mixed to get the second mixture, second is carried out and roasts, obtain nickel cobalt
LiMn2O4 composite material；
The nickle cobalt lithium manganate precursor includes the first presoma and the second presoma, and first presoma is Ni1/3Co1/ 3Mn1/3(OH)2, second presoma includes Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2And Ni0.8Co0.1Mn0.1
(OH)2One of or it is a variety of.
2. preparation method according to claim 1, which is characterized in that first presoma and second presoma
Mass ratio is (3-6): (1-2)；Preferably, the nickle cobalt lithium manganate precursor, the doped compound and the cladding chemical combination
The molar ratio of object is (0.990-0.992): (0.001-0.004): (0.005-0.007)；Preferably, the doped compound with
The molar ratio of the lithium source is 0.02-0.05:1.
3. preparation method according to claim 1, which is characterized in that the lithium source include the carbonate of lithium, hydroxide,
One of oxide, acetate and peroxide are a variety of；Preferably, the doped compound includes the oxide and hydrogen of Mg
One of oxide, the oxide of Ti and hydroxide, the oxide of Zr and hydroxide, the oxide of Al and hydroxide
Or it is a variety of；Preferably, the cladding compound includes oxide and hydroxide, the oxide of Ti and hydroxide, Zr of Zn
Oxide and the mixing of one or more of hydroxide, the oxide of Al and hydroxide.
4. preparation method according to claim 1, which is characterized in that it further include cosolvent in first mixture, institute
State cosolvent include the oxide of B, the oxide of Ba, the oxide of Bi, the oxide of Li, the oxide of K, Na oxide,
One of oxide of the oxide of Ca and Mg is a variety of；It preferably, further include grain refiner in second mixture,
The grain refiner includes one of oxide of the oxide of Ti, the oxide of Nb, the oxide of V and Al or a variety of.
5. preparation method according to claim 1, which is characterized in that the temperature of the first time roasting is 700-1000
DEG C, soaking time 10-20h；The temperature of second of roasting is 650-800 DEG C, soaking time 8-15h.
6. preparation method according to claim 1-5, which is characterized in that first mixture and described second
Mixture is all made of high energy batch mixer and is mixed to get.
7. a kind of nickle cobalt lithium manganate composite material, which is characterized in that use nickle cobalt lithium manganate described in any one of claims 1-6
The preparation method of composite material is made.
8. a kind of lithium battery anode, which is characterized in that be made using nickle cobalt lithium manganate composite material as claimed in claim 7.
9. a kind of preparation method of lithium battery anode according to any one of claims 8 characterized by comprising
The nickle cobalt lithium manganate composite material, conductive agent, binder and solvent are mixed to get slurry, then apply the slurry
It is distributed on substrate, drying obtains the lithium battery anode.
10. preparation method according to claim 9, which is characterized in that the nickle cobalt lithium manganate composite material, the conduction
The mass ratio of agent and the binder is (94-97): (1.5-3): (1.5-3)；The solid content of the slurry is 50-70wt%.
11. preparation method according to claim 9, which is characterized in that the conductive agent includes conductive carbon black, the bonding
Agent includes Kynoar, and the solvent includes N-Methyl pyrrolidone, and the substrate includes aluminium foil.
12. according to the described in any item preparation methods of claim 9-11, which is characterized in that the single side face of the lithium battery anode
Density is 100-200mg/cm2, compacted density 3.1-3.3g/cm3。
13. a kind of lithium battery, which is characterized in that including lithium battery anode according to any one of claims 8.
14. a kind of power supply unit, which is characterized in that including the lithium battery described in claim 13.
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