CN108777295A - A kind of nickel cobalt lithium manganate and preparation method thereof, lithium ion battery - Google Patents
A kind of nickel cobalt lithium manganate and preparation method thereof, lithium ion battery Download PDFInfo
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- CN108777295A CN108777295A CN201810532792.5A CN201810532792A CN108777295A CN 108777295 A CN108777295 A CN 108777295A CN 201810532792 A CN201810532792 A CN 201810532792A CN 108777295 A CN108777295 A CN 108777295A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- 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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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention relates to a kind of nickel cobalt lithium manganate and preparation method thereof, lithium ion batteries, belong to technical field of lithium ion.The nickel cobalt lithium manganate of the present invention is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is oxide, and the nickle cobalt lithium manganate is LiNixCoyMn1‑x‑yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；The oxide is MgO, Al2O3、CaO、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.The nickel cobalt lithium manganate of the present invention can improve aerogenesis phenomenon when high-temperature lithium ion battery storage, fundamentally reduce battery bulging in nickel-cobalt lithium manganate material oxide coated on surface.
Description
Technical field
The present invention relates to a kind of nickel cobalt lithium manganate and preparation method thereof, lithium ion battery, belong to lithium from
Sub- battery technology field.
Background technology
With the continuous quickening of electric automobile market spreading speed, energy of the longer course continuation mileage demand to power battery
Density proposes better challenge.According to the target proposed in national energy-saving and new-energy automobile industrial development planning, until 2020
The energy density of year power battery module reach 300Wh/kg (corresponding single battery energy density be at least up to 330Wh/kg with
On), and the key for solving power battery energy density is then the breakthrough of battery material technology.
Currently, for domestic and international most of power battery enterprise, nickelic or high voltage is to improve battery energy density
The only way which must be passed.However, the problem of can not be ignored existing for this two lines is equal is aerogenesis problem.Nickelic ternary material stratiform
Structure positive electrode belongs to hexagonal structure as cobalt acid lithium, and gram volume is higher relative to cobalt acid lithium, and actual capacity can be with
Reach 190~200mAh/g, but its practical compacted density is only 3.6g/cm3.The application of nickelic Layered Structural Positive Electrode Materials is still
There are many problems, limit the main reason for nickelic Layered Structural Positive Electrode Materials are applied in a lithium ion secondary battery be its
High temperature aerogenesis in lithium rechargeable battery, such high temperature aerogenesis can make flexible packing lithium ion secondary battery volume expansion, meeting
Box hat lithium rechargeable battery internal pressure is set to increase, to bring serious security risk.
In high-voltage battery, while positive electrode charging voltage improves, the oxygenolysis phenomenon of electrolyte can add
Play leads to battery bulging, so as to cause battery performance deterioration and there are larger security risks.Under high voltages, anode is living
Property material oxidation activity it is higher so that its reactivity between electrolyte increases, plus at high temperature, high-voltage anode with
Reaction between electrolyte is further exacerbated by, and is caused the oxidative degradation products of electrolyte constantly to be deposited in positive electrode surface, is deteriorated
Positive electrode surface characteristic causes the internal resistance of battery and thickness constantly to increase.
High-voltage battery goes back the phenomenon that generally existing cathode metal Ion release in use, and especially battery is passing through
After crossing prolonged high temperature storage, the dissolution of cathode metal ion is further exacerbated by, and the capacity of battery is caused to keep relatively low.One side
Face, at high temperature, the LiPF in electrolyte6It is easy to decompose, generates HF and PF5.Wherein HF can corrode anode, cause metal from
The dissolution of son causes capacity to be lost in destroy cathode material structure.In addition, the Li on positive electrode surface2CO3It can occur with HF
Reaction generates CO2, so as to cause battery bulging.On the other hand, under high voltages, electrolyte is easy to be aoxidized in anode, causes
The metal ion of positive active material is easy to be reduced and dissolve out in electrolyte, to destroy cathode material structure, causes to hold
Amount loss.Meanwhile dissolution easily propagates through SEI films and reaches cathode acquisition electronics and be reduced into gold to the metal ion of electrolyte
Belong to simple substance causes cathode impedance constantly to increase to destroy the structure of SEI films, and self-discharge of battery aggravation, irreversible capacity increases
Greatly, penalty.
Application publication number is that the Chinese invention patent of CN107240690A discloses a kind of cladded type lithium ion battery ternary
The preparation method of positive electrode, this method is by the way that nano-oxide to be distributed in isopropanol, ethyl alcohol or acetone, nano-oxide
For nano silicon dioxide or nano zirconium dioxide, the dispersion liquid after dispersion and tertiary cathode material LiNixCoyMnzO2(0.5≤x
≤ 0.6,0.1≤y≤0.2,0.2≤z≤0.3, x+y+z=1) mixing, the mixture stirred to get is dry, is sintered, and is wrapped
Cover type ternary cathode material of lithium ion battery.The cladded type lithium ion battery ternary material is using ternary material as core, surface cladding
Oxide, but the oxide type of its cladding is only limitted to nano silicon dioxide and nano zirconium dioxide, which has
Preferable cycle performance, high rate performance still can not inhibit high-temperature lithium ion battery aerogenesis.
Invention content
The purpose of the present invention is to provide a kind of nickle cobalt lithium manganate that can weaken high-temperature lithium ion battery aerogenesis is compound just
Pole material.
It is another object of the present invention to provide a kind of preparation methods of above-mentioned composite positive pole.The present invention's is another
It is a to be designed to provide a kind of lithium ion battery using above-mentioned composite positive pole.
To achieve the above object, the technical solution of nickel cobalt lithium manganate of the invention is：
A kind of nickel cobalt lithium manganate is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is oxide；It is described
Nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；The oxide is MgO, Al2O3、
CaO、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.
The nickel cobalt lithium manganate of the present invention is in nickel-cobalt lithium manganate material oxide coated on surface, and oxide
In type be related to alkaline earth oxide, transition metal oxide etc..These oxides are coated on nickel-cobalt lithium manganate material
Grain surface can play the promotion of the cycle performance of lithium ion battery, high rate performance, specific capacity, thermal stability etc. promotion and make
With.Most of all, the composite positive pole of the present invention can improve aerogenesis phenomenon when high-temperature lithium ion battery stores, from root
Battery bulging is reduced in sheet.
The nickel cobalt lithium manganate is second particle.The second particle is made of primary particle, primary
Grain is above-mentioned nucleocapsid.Second particle is spherical or spherical.The grain size of the primary particle is 0.3-2 μm.Described two
The grain size of secondary particle is 3-18 μm.
The covering amount of oxide controls in smaller range, and general control is within the scope of 500-3000ppm.It is i.e. described
The mass ratio of shell and core is 5-30:10000.Oxide covering amount is smaller, and the thickness that can control shell structure is smaller.In general,
The thickness of the shell is 200-2000nm.The shell structure of this thickness, can make oxide play its chemical property and
It is played in the performance for influencing the ternary material as core.
Nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, the value of x, y are preferably x=1/3 and y=1/3, x=0.6 and y=
0.2, x=0.5 and y=0.2, x=0.4 and y=0.4, x=0.4 and y=0.2 or x=0.8 and y=0.1.It is corresponding, nickel
Cobalt manganic acid lithium is NCM111, NCM622, NCM523, NCM442, NCM424 or NCM811.
The preparation method technical solution of nickel cobalt lithium manganate of the present invention is：
A kind of preparation method of nickel-cobalt lithium manganate cathode material, includes the following steps：
1) nickel-cobalt lithium manganate material is uniformly mixed with oxide in an inert gas atmosphere, obtains mixing material；It is described
Nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；The oxide is MgO, Al2O3、
CaO、SiO2、ZrO2、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of；
2) mixing material for obtaining step 1) is in having oxygen atmosphere, sintering, it is cooling to get.
The preparation method of the present invention is easy to operate, and simple process is convenient for large-scale industrial production.Above-mentioned nickel cobalt manganese
Sour lithium material be uniformly mixed with oxide be solid particle direct mixing, the complexity of operation can be greatly lowered.
Described be sintered at 500 DEG C is sintered 5h.
Inert atmosphere when nickle cobalt lithium manganate is mixed with oxide uses existing inert gas, in general, above-mentioned
Inert gas is nitrogen or argon gas.
It is described to have oxygen atmosphere for the atmosphere containing oxygen.The usually mixed gas of oxygen or oxygen and inert gas.
Described be uniformly mixed mixes for nickel-cobalt lithium manganate material is carried out high-speed flow with oxide.The high-speed flow is mixed
Conjunction is carried out in high-speed flow mixing machine.
The oxide is nano-oxide.The usage amount of above-mentioned oxide accounts for the 0.05- of nickel-cobalt lithium manganate material quality
0.3%.
The nickel-cobalt lithium manganate material is made by the method included the following steps：By nickel cobalt manganese manganate precursor for lithium
(NixCoyMn1-x-y)(OH)2It is uniformly mixed with lithium source, wherein 0<x<1,0<y<1,0<1-x-y<1；Then in the case where there is oxygen atmosphere,
800-1000 DEG C sintering 15-20h to get.
The lithium source is LiOH, Li2CO3One or more of.
The sum of molal quantity of nickel, cobalt, manganese element and the ratio of the molal quantity of lithium in lithium source are in the nickel-cobalt lithium manganate material
1:1.05。
It is first warming up to 300-500 DEG C before the 800-1000 DEG C of sintering, keeps the temperature 2-5h.Be warming up to 300-500 DEG C use
Heating rate is 5-15 DEG C/min.
It is cooled down after above-mentioned 800-1000 DEG C of sintering.The cooling is to be cooled to 50-100 DEG C.
Nickel cobalt manganese manganate precursor for lithium (the NixCoyMn1-x-y)(OH)2It is made by the method included the following steps：By water
Insoluble nickel salt, water soluble cobaltous salt, water-soluble manganese salt hybrid reaction in water, be separated by solid-liquid separation to get.The hybrid reaction is in precipitating reagent
It is carried out under the conditions of existing.
The precipitating reagent is preferably sodium hydroxide, further preferably sodium hydroxide solution.Above-mentioned hybrid reaction is in pattern control
It is carried out under the conditions of preparation is existing.The pattern controlling agent is ammonium hydroxide.
The water soluble nickel salt is nickel sulfate.The water soluble cobaltous salt is cobaltous sulfate.The water-soluble manganese salt is manganese sulfate.
The molar ratio of the manganese of the cobalt in nickel, water soluble cobaltous salt, water-soluble manganese salt in the water soluble nickel salt according to
(NixCoyMn1-x-y)(OH)2In ratio setting, as x：y：(1-x-y).
Water soluble nickel salt, precipitating reagent, pattern controlling agent molar ratio be 2：2：1.
The usage amount of water be so that water soluble nickel salt, water soluble cobaltous salt, water-soluble manganese salt be dissolved in water after, nickel ion, cobalt from
The sum of concentration of son and manganese ion is 2mol/L.
Water soluble nickel salt, water soluble cobaltous salt, water-soluble manganese salt and precipitating reagent, pattern controlling agent in water hybrid reaction when
PH is 10.8-11.2.
The reaction temperature of the hybrid reaction is 50 DEG C.The time of the hybrid reaction is 12h.It is aged after hybrid reaction
2h。
It is separated by solid-liquid separation after ageing.
It washed, dried after separation of solid and liquid.Dry is vacuum drying.
Dry temperature is 120 DEG C.The dry time is 8h.
The technical solution of lithium ion battery of the present invention is：
A kind of lithium ion battery, including positive plate, negative plate, the positive plate include plus plate current-collecting body and are coated in positive
The positive electrode material layer of collection liquid surface, the positive electrode material layer include positive active material, and the positive active material is nickel cobalt
Lithium manganate composite anode material；The nickel cobalt lithium manganate is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is oxygen
Compound；The nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；The oxide is
MgO、Al2O3、CaO、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.
The nickel cobalt lithium manganate is second particle.The second particle is made of primary particle, primary
Grain is above-mentioned nucleocapsid.Second particle is spherical or spherical.The grain size of the primary particle is 0.3-2 μm.Described two
The grain size of secondary particle is 3-18 μm.
The covering amount of oxide controls in smaller range, and general control is within the scope of 500-3000ppm.It is i.e. described
The mass ratio of core and shell is 5-30:10000.Oxide covering amount is smaller, and the thickness that can control shell structure is smaller.In general,
The thickness of the shell is 200-2000nm.The shell structure of this thickness, can make oxide play its chemical property and
It is played in the performance for influencing the ternary material as core.
Nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, the value of x, y are preferably x=1/3 and y=1/3, x=0.6 and y=
0.2, x=0.5 and y=0.2, x=0.4 and y=0.4, x=0.4 and y=0.2 or x=0.8 and y=0.1.It is corresponding, nickel
Cobalt manganic acid lithium is NCM111, NCM622, NCM523, NCM442, NCM424 or NCM811.
Method in the prior art may be used in the preparation method of the lithium ion battery of the present invention.
The beneficial effects of the invention are as follows：
The nickel cobalt lithium manganate of the present invention can improve the interface temperature of positive electrode, optimize material knot
Structure reduces the residual lithium of material surface, battery bulging can be solved the problems, such as from source.
Specific implementation mode
Technical scheme of the present invention is described further with reference to specific embodiment.
Embodiment 1
The nickel cobalt lithium manganate of the present embodiment is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is metal oxygen
Compound.Nucleocapsid mass ratio is 99.88:0.12.The molecular formula of nickle cobalt lithium manganate is Li (Ni0.8Co0.1Mn0.1)O2.Metal oxide
For aluminium oxide (Al2O3).The thickness of shell is 200nm.The composite positive pole is second particle, and the second particle is by primary particle
It constitutes.The grain size of primary particle is 0.3 μm, and the grain size of second particle is 3 μm.
The preparation method of the nickel cobalt lithium manganate of the present embodiment includes the following steps：
1) according to molecular formula Li (Ni0.8Co0.1Mn0.1)O2The molar ratio Ni of middle transition metal element：Co：Mn=8:1:1
Take NiSO4、CoSO4、MnSO4, it is then dissolved in water and obtains mixed solution, cationic total concentration is 2mo1/ in mixed solution
L。
2) mixed solution that step 1) obtains is added drop-wise to the reaction vessel full of nitrogen atmosphere with the speed of 0.2L/h
In.Then sodium hydroxide solution and ammonium hydroxide are added dropwise thereto, using method regulation system pH=11.0 in the prior art ±
0.2；A concentration of 2mol/L of sodium hydroxide solution, a concentration of 3mol/L of ammonium hydroxide.Then heating water bath reacts 12h to 50 DEG C
Afterwards, it is aged 2h；Filtering, washing are dried in vacuo 8h at 120 DEG C, obtain nickel cobalt manganese hydroxide precursor powder.
3) the nickel cobalt manganese hydroxide precursor powder for obtaining step 2) and lithium hydroxide are according to molar ratio Li/ (Ni+Co
+ Mn)=1.05:1 ratio is uniformly mixed, and is placed in sintering furnace, under oxygen atmosphere, with the heating rate liter of 5 DEG C/min
Temperature keeps the temperature 2h to after 300 DEG C；Then it is further heated up to 800 DEG C of sintering 20h.Then proceed to be passed through oxygen be cooled to 100 DEG C with
Lower taking-up is ground, and screening obtains the Li (Ni with layered crystal structure0.8Co0.1Mn0.1)O2Positive electrode.
4) Li (Ni for obtaining step 3)0.8Co0.1Mn0.1)O2Positive electrode and nanometer Al2O3Powder is according to 99.88:
0.12 mass ratio mixing, is subsequently placed in high-speed flow mixing machine, is passed through high pure nitrogen, replace three times, until high-speed flow is mixed
Nitrogen gas purity is more than 99% in conjunction machine；Then with the rotating speed mixing 5min of 2000rmp, a nanometer AL is obtained2O3The Li of cladding
(Ni0.8Co0.1Mn0.1)O2Positive electrode material precursor.
5) the nanometer AL for obtaining step 4)2O3Li (the Ni of cladding0.8Co0.1Mn0.1)O2Positive electrode material precursor is placed in gas
In atmosphere stove, in oxygen atmosphere, it is sintered 5h at 500 DEG C, is taken out after being then cooled to 100 DEG C, sieves, obtain a nanometer AL2O3Cladding
Li (Ni0.8Co0.1Mn0.1)O2Positive electrode.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and positive plate includes anode collection
Body and coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer includes positive active material, and positive active material is
Above-mentioned nanometer AL2O3Li (the Ni of cladding0.8Co0.1Mn0.1)O2Positive electrode.Negative electrode active material used is artificial on negative plate
Graphite.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
1) by above-mentioned nanometer AL2O3The positive electrode of cladding is with conductive agent SP, binder PVDF according to 95.5:2.5:2 matter
Amount is uniformly mixed than being added in solvent, and the anode sizing agent that solid content is 65% is made, and wherein solvent is NMP.The slurry is uniform
Ground is coated in the aluminium foil two sides of 12 μ m-thicks, dry, using roll squeezer roll-in, obtains positive plate.The compacted density of positive plate is
3.3g/cm3。
2) use specific surface area for 3.1m2The artificial graphite of/g is as negative electrode active material, with SBR (the poly- fourth rubbers of styrene
Glue) with the mixture of CMC (sodium carboxymethylcellulose) it is binder, the mass ratio of SBR and CMC refer to the prior art；With conduction
Carbon black is as conductive agent；The mass ratio of negative electrode active material and binder, conductive agent is 95.8:3.2:1, using water as solvent, close
Slurry prepares negative electrode slurry；The mass fraction of solvent is 55% in negative electrode slurry.Then the negative electrode slurry is coated uniformly on 8 μ m-thicks
Copper foil two sides, it is dry, carry out roller process using roll squeezer, obtain negative plate, the compacted density of negative plate is 1.6g/
cm3。
3) conductive lug will be welded on positive plate obtained and negative plate, the PP/PE composite diaphragms for being 16 μm with thickness are
Diaphragm, it is stacked according to the sequence of positive plate, diaphragm, negative plate, diaphragm, it is wound into spiral battery core, is suppressed, it is multiple to be packed into aluminum plastic film
In condensation material packaging bag, the film thickness of packaging bag is 115 μm.Nonaqueous electrolytic solution is injected into packaging bag, is sealed, and chemical conversion waits for positive and negative
After extremely abundant aerogenesis, extract out packaging bag in gas, cut off extra packaging bag part, obtain size be 3mm × 125mm ×
The soft-package battery of 140mm.The electrolyte of injection is the LiPF of 1mol/L6Solution, wherein solvent are the mixing of EC, PC, DEC composition
Solvent.
Embodiment 2
The nickel cobalt lithium manganate of the present embodiment is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is metal oxygen
Compound.Nucleocapsid mass ratio is 99.88:0.12.The molecular formula of nickle cobalt lithium manganate is Li (Ni0.8Co0.1Mn0.1)O2.Metal oxide
For zirconium oxide (ZrO2).The thickness of shell is 2000nm.The composite positive pole is second particle, and the second particle is by primary particle
It constitutes.The grain size of primary particle is 2 μm, and the grain size of second particle is 18 μm.
The preparation method of the nickel cobalt lithium manganate of the present embodiment includes the following steps：
1) according to molecular formula Li (Ni0.8Co0.1Mn0.1)O2The molar ratio Ni of middle transition metal element：Co：Mn=8:1:1
Take NiSO4、CoSO4、MnSO4, it is then dissolved in water and obtains mixed solution, cationic total concentration is 2mo1/ in mixed solution
L。
2) mixed solution that step 1) obtains is added drop-wise to the reaction vessel full of nitrogen atmosphere with the speed of 0.2L/h
In.Then sodium hydroxide solution and ammonium hydroxide are added dropwise thereto, using method regulation system pH=11.0 in the prior art ±
0.2；A concentration of 2mol/L of sodium hydroxide solution, a concentration of 3mol/L of ammonium hydroxide.Then heating water bath reacts 12h to 50 DEG C
Afterwards, it is aged 2h；Filtering, washing are dried in vacuo 8h at 120 DEG C, obtain nickel cobalt manganese hydroxide precursor powder.
3) the nickel cobalt manganese hydroxide precursor powder for obtaining step 2) and lithium hydroxide are according to molar ratio Li/ (Ni+Co
+ Mn)=1.05:1 ratio is uniformly mixed, and is placed in sintering furnace, under oxygen atmosphere, with the heating rate liter of 5 DEG C/min
Temperature keeps the temperature 2h to after 300 DEG C；Then it is further heated up to 1000 DEG C of sintering 15h.It then proceedes to be passed through oxygen and is cooled to 100 DEG C
It takes out, grinds below, screening obtains the Li (Ni with layered crystal structure0.8Co0.1Mn0.1)O2Positive electrode.
4) Li (Ni for obtaining step 3)0.8Co0.1Mn0.1)O2Positive electrode and ZrO2Powder is according to 99.88:0.12 matter
Amount is subsequently placed in than mixing in high-speed flow mixing machine, is passed through high pure nitrogen, is replaced three times, until nitrogen in high speed airflow mixer
Gas purity is more than 99%；Then with the rotating speed mixing 5min of 2000rmp, ZrO is obtained2Li (the Ni of cladding0.8Co0.1Mn0.1)O2Just
Pole material precursor.
5) ZrO for obtaining step 4)2Li (the Ni of cladding0.8Co0.1Mn0.1)O2Positive electrode material precursor is placed in atmosphere furnace
In, in oxygen atmosphere, it is sintered 5h at 500 DEG C, is taken out after being then cooled to 100 DEG C, sieves, obtains ZrO2The Li of cladding
(Ni0.8Co0.1Mn0.1)O2Positive electrode.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and positive plate includes anode collection
Body and coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer includes positive active material, and positive active material is
Above-mentioned ZrO2Li (the Ni of cladding0.8Co0.1Mn0.1)O2Positive electrode.Negative electrode active material used is artificial graphite on negative plate.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
1) by above-mentioned ZrO2The positive electrode of cladding is with conductive agent SP, binder PVDF according to 95.5:2.5:2 mass ratio
It is added in solvent and is uniformly mixed, the anode sizing agent that solid content is 65% is made, wherein solvent is NMP.The slurry is equably applied
The aluminium foil two sides of 12 μ m-thicks is overlayed on, it is dry, using roll squeezer roll-in, obtain positive plate.The compacted density of positive plate is 3.3g/
cm3。
2) use specific surface area for 3.1m2The artificial graphite of/g is as negative electrode active material, with SBR (the poly- fourth rubbers of styrene
Glue) with the mixture of CMC (sodium carboxymethylcellulose) it is binder, the mass ratio of SBR and CMC refer to the prior art；With conduction
Carbon black is as conductive agent；The mass ratio of negative electrode active material and binder, conductive agent is 95.8:3.2:1, using water as solvent, close
Slurry prepares negative electrode slurry；The mass fraction of solvent is 55% in negative electrode slurry.Then the negative electrode slurry is coated uniformly on 8 μ m-thicks
Copper foil two sides, it is dry, carry out roller process using roll squeezer, obtain negative plate, the compacted density of negative plate is 1.6g/
cm3。
3) conductive lug will be welded on positive plate obtained and negative plate, the PP/PE composite diaphragms for being 16 μm with thickness are
Diaphragm, it is stacked according to the sequence of positive plate, diaphragm, negative plate, diaphragm, it is wound into spiral battery core, is suppressed, it is multiple to be packed into aluminum plastic film
In condensation material packaging bag, the film thickness of packaging bag is 115 μm.Nonaqueous electrolytic solution is injected into packaging bag, is sealed, and chemical conversion waits for positive and negative
After extremely abundant aerogenesis, extract out packaging bag in gas, cut off extra packaging bag part, obtain size be 3mm × 125mm ×
The soft-package battery of 140mm.The electrolyte of injection is the LiPF of 1mol/L6Solution, wherein solvent are the mixing of EC, PC, DEC composition
Solvent.
Embodiment 3
The nickel cobalt lithium manganate of the present embodiment is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is metal oxygen
Compound.Nucleocapsid mass ratio is 99.88:0.12.The molecular formula of nickle cobalt lithium manganate is Li (Ni0.8Co0.1Mn0.1)O2.Metal oxide
For titanium dioxide (TiO2).The thickness of shell is 1000nm.The composite positive pole is second particle, and the second particle is by primary
Grain is constituted.The grain size of primary particle is 0.8 μm, and the grain size of second particle is 10 μm.
The preparation method of the nickel cobalt lithium manganate of the present embodiment includes the following steps：
1) according to molecular formula Li (Ni0.8Co0.1Mn0.1)O2The molar ratio Ni of middle transition metal element：Co：Mn=8:1:1
Take NiSO4、CoSO4、MnSO4, it is then dissolved in water and obtains mixed solution, cationic total concentration is 2mo1/ in mixed solution
L。
2) mixed solution that step 1) obtains is added drop-wise to the reaction vessel full of nitrogen atmosphere with the speed of 0.2L/h
In.Then sodium hydroxide solution and ammonium hydroxide are added dropwise thereto, using method regulation system pH=11.0 in the prior art ±
0.2；A concentration of 2mol/L of sodium hydroxide solution, a concentration of 3mol/L of ammonium hydroxide.Then heating water bath reacts 12h to 50 DEG C
Afterwards, it is aged 2h；Filtering, washing are dried in vacuo 8h at 120 DEG C, obtain nickel cobalt manganese hydroxide precursor powder.
3) the nickel cobalt manganese hydroxide precursor powder for obtaining step 2) and lithium hydroxide are according to molar ratio Li/ (Ni+Co
+ Mn)=1.05:1 ratio is uniformly mixed, and is placed in sintering furnace, under oxygen atmosphere, with the heating rate liter of 5 DEG C/min
Temperature keeps the temperature 2h to after 300 DEG C；Then it is further heated up to 900 DEG C of sintering 18h.Then proceed to be passed through oxygen be cooled to 100 DEG C with
Lower taking-up is ground, and screening obtains the Li (Ni with layered crystal structure0.8Co0.1Mn0.1)O2Positive electrode.
4) Li (Ni for obtaining step 3)0.8Co0.1Mn0.1)O2Positive electrode and TiO2Powder is according to 99.88:0.12 matter
Amount is subsequently placed in than mixing in high-speed flow mixing machine, is passed through high pure nitrogen, is replaced three times, until nitrogen in high speed airflow mixer
Gas purity is more than 99%；Then with the rotating speed mixing 5min of 2000rmp, TiO is obtained2Li (the Ni of cladding0.8Co0.1Mn0.1)O2Just
Pole material precursor.
5) TiO for obtaining step 4)2Li (the Ni of cladding0.8Co0.1Mn0.1)O2Positive electrode material precursor is placed in atmosphere furnace
In, in oxygen atmosphere, it is sintered 5h at 500 DEG C, is taken out after being then cooled to 100 DEG C, sieves, obtains TiO2The Li of cladding
(Ni0.8Co0.1Mn0.1)O2Positive electrode.
The lithium ion battery of the present embodiment includes positive plate, negative plate, diaphragm, electrolyte, and positive plate includes anode collection
Body and coated in the positive electrode material layer on plus plate current-collecting body, positive electrode material layer includes positive active material, and positive active material is
Above-mentioned TiO2Li (the Ni of cladding0.8Co0.1Mn0.1)O2Positive electrode.Negative electrode active material used is artificial graphite on negative plate.
The preparation method of the lithium ion battery of the present embodiment includes the following steps：
1) by above-mentioned TiO2The positive electrode of cladding is with conductive agent SP, binder PVDF according to 95.5:2.5:2 mass ratio
It is added in solvent and is uniformly mixed, the anode sizing agent that solid content is 65% is made, wherein solvent is NMP.The slurry is equably applied
The aluminium foil two sides of 12 μ m-thicks is overlayed on, it is dry, using roll squeezer roll-in, obtain positive plate.The compacted density of positive plate is 3.3g/
cm3。
2) use specific surface area for 3.1m2The artificial graphite of/g is as negative electrode active material, with SBR (the poly- fourth rubbers of styrene
Glue) with the mixture of CMC (sodium carboxymethylcellulose) it is binder, the mass ratio of SBR and CMC refer to the prior art；With conduction
Carbon black is as conductive agent；The mass ratio of negative electrode active material and binder, conductive agent is 95.8:3.2:1, using water as solvent, close
Slurry prepares negative electrode slurry；The mass fraction of solvent is 55% in negative electrode slurry.Then the negative electrode slurry is coated uniformly on 8 μ m-thicks
Copper foil two sides, it is dry, carry out roller process using roll squeezer, obtain negative plate, the compacted density of negative plate is 1.6g/
cm3。
3) conductive lug will be welded on positive plate obtained and negative plate, the PP/PE composite diaphragms for being 16 μm with thickness are
Diaphragm, it is stacked according to the sequence of positive plate, diaphragm, negative plate, diaphragm, it is wound into spiral battery core, is suppressed, it is multiple to be packed into aluminum plastic film
In condensation material packaging bag, the film thickness of packaging bag is 115 μm.Nonaqueous electrolytic solution is injected into packaging bag, is sealed, and chemical conversion waits for positive and negative
After extremely abundant aerogenesis, extract out packaging bag in gas, cut off extra packaging bag part, obtain size be 3mm × 125mm ×
The soft-package battery of 140mm.The electrolyte of injection is the LiPF of 1mol/L6Solution, wherein solvent are the mixing of EC, PC, DEC composition
Solvent.
Embodiment 4
The present embodiment difference from example 1 is that, using oxide B2O3Metal oxidation in alternative embodiment 1
Object nanometer Al2O3, other identical as in embodiment 1.
Embodiment 5
The present embodiment difference from example 1 is that, nickel cobalt lithium manganate center shell mass ratio is
99.92:0.08, in the preparation method of nickel cobalt lithium manganate, obtained Li (Ni0.8Co0.1Mn0.1)O2Anode
Material and nanometer Al2O3Powder is according to 99.92:0.08 mass ratio mixing, it is other identical as in embodiment 1.
Embodiment 6
The present embodiment difference from example 1 is that, nickel cobalt lithium manganate center shell mass ratio is
99.84:0.16, in the preparation method of nickel cobalt lithium manganate, obtained Li (Ni0.8Co0.1Mn0.1)O2Anode
Material and nanometer Al2O3Powder is according to 99.84:0.16 mass ratio mixing, it is other identical as in embodiment 1.
Embodiment 7
The present embodiment difference from example 1 is that, nickel cobalt lithium manganate center shell mass ratio is
99.80:0.20, in the preparation method of nickel cobalt lithium manganate, obtained Li (Ni0.8Co0.1Mn0.1)O2Anode
Material and nanometer Al2O3Powder is according to 99.80:0.20 mass ratio mixing, it is other identical as in embodiment 1.
Embodiment 8
The present embodiment difference from example 1 is that, in the preparation method of nickel cobalt lithium manganate,
Nitrogen gas purity is 80% in high-speed flow mixing machine, other identical as in embodiment 1.
Embodiment 9
The present embodiment difference from example 1 is that, in the preparation method of nickel cobalt lithium manganate,
Nitrogen gas purity is 90% in high-speed flow mixing machine, other identical as in embodiment 1.
Embodiment 10
The present embodiment difference from example 1 is that, using the nanometer Al in CaO alternative embodiments 12O3, other
It is identical as in embodiment 1.
Embodiment 11
The present embodiment difference from example 1 is that, using SiO2Nanometer Al in alternative embodiment 12O3, other
It is equal identical as in embodiment 1.
Embodiment 12
The present embodiment difference from example 1 is that, using the nanometer Al in ZnO alternative embodiments 12O3, other
It is identical as in embodiment 1.
Embodiment 13
The present embodiment difference from example 1 is that, using the nanometer Al in SnO alternative embodiments 12O3, other
It is identical as in embodiment 1.
Embodiment 14
The present embodiment difference from example 1 is that, using Bi2O3Nanometer Al in alternative embodiment 12O3, other
It is equal identical as in embodiment 1.
Embodiment 15
The present embodiment difference from example 1 is that, in nickel cobalt lithium manganate, as nuclear material
Nickle cobalt lithium manganate is Li (Ni0.6Co0.2Mn0.2)O2, correspondingly, in the preparation method of nickel cobalt lithium manganate, press
According to molecular formula Li (Ni0.6Co0.2Mn0.2)O2The molar ratio Ni of middle transition metal element：Co：Mn=6:2:2 take NiSO4、
CoSO4、MnSO4, other identical as in embodiment 1.
Embodiment 16
The present embodiment difference from example 1 is that, in nickel cobalt lithium manganate, as nuclear material
Nickle cobalt lithium manganate is Li (Ni0.5Co0.2Mn0.3)O2, correspondingly, in the preparation method of nickel cobalt lithium manganate, press
According to molecular formula Li (Ni0.5Co0.2Mn0.3)O2The molar ratio Ni of middle transition metal element：Co：Mn=5:2:3 take NiSO4、
CoSO4、MnSO4, other identical as in embodiment 1.
Comparative example 1
This comparative example is that the nitrogen protection gas in step 4) is replaced with normal atmospheric ring on the basis of embodiment 1
It is other same as Example 1 under border.Then Soft Roll electricity is prepared using nickel cobalt lithium manganate made from this method
Pond.
Comparative example 2
This comparative example is on the basis of embodiment 1, by step 4) -5) encapsulation steps save, i.e.,
LiNi0.8Co0.1Mn0.1O2Material is other same as Example 1 without cladding processing.Then using obtaining
LiNi0.8Co0.1Mn0.1O2Positive electrode makes soft-package battery.
Test example
(1) volume test
Lithium ion battery made of nickel cobalt lithium manganate in Example 1-9 and comparative example, in 2.8-
4.2V voltage ranges discharge according to 0.3C chargings, 0.3C, measure its capacity and calculate the specific capacity (unit of composite positive pole
The capacity that mass activity substance is released).
Test result is as shown in table 1.
(2) lithium carbonate content measurement
Nickel cobalt lithium manganate in Example 1-9 and comparative example is surveyed as follows as sample
Measure the carbonic acid lithium content on material granule surface：
1) it weighs in 30.00g samples to conical flask, add 100mL boils the ultra-pure water being cooled to room temperature；
2) magnetic agitation rotor is added, closes the lid, is placed on magnetic stirring apparatus and stirs 30min；
3) it after the completion of stirring, pours into ready Buchner funnel and is filtered；
4) it weighs in filtrate 25.00g to 100mL beakers, then weighs 55.00g ultra-pure waters and be added thereto, electrode and spiral
Blender is inserted into filtrate, is detected using automatic potentiometric titration.
Test result is as shown in table 1.
(3) high-temperature storage performance is tested
Lithium ion soft-package battery in embodiment 1-9 and comparative example is measured into its thickness change and guarantor in accordance with the following steps
It holds capacity and restores capacity.
Battery after chemical conversion is charged to 4.2V with 1C constant current constant voltages at normal temperatures, measures initial battery thickness, initial discharge
Then capacity stores 7 days at 55 DEG C.Battery is cooled to room temperature and surveys battery final thickness again, calculates cell thickness expansion rate.
Calculation formula is as follows：
Cell thickness expansion rate (%)=(final thickness-original depth)/original depth × 100%
Then the holding capacity and recovery capacity that 2.8V measures battery are discharged to 1C.
Test result is as shown in table 1.
The performance test results of 1 embodiment 1-9 of table and nickel cobalt manganese composite positive pole and lithium ion battery in comparative example 2
As shown in Table 1, LiNi0.8Co0.1Mn0.1O2Positive electrode surface carbonic acid lithium content is to soft-package battery high temperature storage
There can be larger impact.The LiNi that the present invention passes through cladding0.8Co0.1Mn0.1O2Positive electrode can be obviously improved the production of high temperature storage
Gas situation, and pass through nanometer Al2O3Cladding is to LiNi0.8Co0.1Mn0.1O2Positive electrode gram volume wields influence minimum, and right
There is optimal improvement in high temperature storage aerogenesis.
(4) influence of process nitrogen content is coated
It is coated in atmosphere to using different nitrogen content in embodiment 1, embodiment 8 and 9 and comparative example 1
The performance of composite positive pole is compared, and comparing result is shown in Table 2.
Influence of the different nitrogen content to material property during the cladding of table 2
It can be seen from Table 2 that in nanometer Al2O3Coat LiNi0.8Co0.1Mn0.1O2In materials process, different atmosphere is to material
Material surface carbonic acid lithium content has larger impact.As can be seen from the table, material can be significantly reduced by being passed through nitrogen during cladding
With the CO in air2Contact to avoid material surface from generating lithium carbonate, and then has significantly the high-temperature storage performance of battery
It is promoted.
Claims (10)
1. a kind of nickel cobalt lithium manganate is nucleocapsid, core is nickle cobalt lithium manganate, and shell is oxide, feature
It is, the nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；The oxide is
MgO、Al2O3、CaO、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.
2. nickel cobalt lithium manganate according to claim 1, which is characterized in that the mass ratio of the shell and core
For 5-30:10000.
3. a kind of preparation method of nickel cobalt lithium manganate, it is characterised in that：Include the following steps：
1) nickel-cobalt lithium manganate material is uniformly mixed with oxide in an inert gas atmosphere, obtains mixing material；The nickel cobalt
LiMn2O4 is LiNixCoyMn1-x-yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；The oxide is MgO, Al2O3、CaO、
SiO2、ZrO2、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of；
2) mixing material for obtaining step 1) is in having oxygen atmosphere, sintering, it is cooling to get.
4. the preparation method of nickel cobalt lithium manganate according to claim 3, which is characterized in that the mixing
It is uniformly that nickel-cobalt lithium manganate material is carried out high-speed flow with oxide to mix.
5. the preparation method of nickel cobalt lithium manganate according to claim 3, which is characterized in that the oxidation
The quality of object is the 0.05-0.3% of nickel-cobalt lithium manganate material quality.
6. the preparation method of the nickel cobalt lithium manganate according to claim 3-5 any one, feature exist
In the nickel-cobalt lithium manganate material is made by the method included the following steps：By nickel cobalt manganese manganate precursor for lithium
(NixCoyMn1-x-y)(OH)2It is uniformly mixed with lithium source, wherein 0<x<1,0<y<1,0<1-x-y<1；Then in the case where there is oxygen atmosphere,
800-1000 DEG C sintering 15-20h to get.
7. the preparation method of nickel cobalt lithium manganate according to claim 6, which is characterized in that the lithium source
For LiOH, Li2CO3One or more of.
8. the preparation method of nickel cobalt lithium manganate according to claim 6, which is characterized in that the nickel cobalt
The ratio of the sum of molal quantity of nickel, cobalt, manganese element and the molal quantity of lithium in lithium source is 1 in lithium manganate material:1.05.
9. the preparation method of nickel cobalt lithium manganate according to claim 6, which is characterized in that the 800-
It is first warming up to 300-500 DEG C before 1000 DEG C of sintering, keeps the temperature 2-5h.
10. a kind of lithium ion battery, including positive plate, negative plate, the positive plate includes plus plate current-collecting body and is coated in positive
The positive electrode material layer of collection liquid surface, the positive electrode material layer include positive active material, and the positive active material is nickel cobalt
Lithium manganate composite anode material；The nickel cobalt lithium manganate is nucleocapsid, and core is nickle cobalt lithium manganate, and shell is oxygen
Compound, which is characterized in that the nickle cobalt lithium manganate is LiNixCoyMn1-x-yO2, wherein 0<x<1,0<y<1,0<1-x-y<1；Institute
It is MgO, Al to state oxide2O3、CaO、ZnO、TiO2、SnO、B2O3、Bi2O3One or more of.
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| CN113830846A (en) * | 2021-11-24 | 2021-12-24 | 湖南长远锂科股份有限公司 | Coating modified cathode material and preparation method thereof |
| WO2023130828A1 (en) * | 2022-01-04 | 2023-07-13 | 广东邦普循环科技有限公司 | High-temperature stable positive electrode material, and preparation method therefor and application thereof |
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