CN110085831A - A kind of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof - Google Patents
A kind of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof Download PDFInfo
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- 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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Abstract
It is to be coated with metatitanic acid lithium on the surface of kernel using nickel-cobalt-manganternary ternary anode material as kernel, and add chelating agent during cladding to promote to coat the invention discloses a kind of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof.Resulting materials of the present invention, spinel structure metatitanic acid lithium crystal structure during lithium ion is embedded in deintercalation are able to maintain the stability of height, have good cycle life, effectively prevent the formation and lithium metal deposition of SEI film, and Li2TiO3The conductivity of lithium ion can not only be improved, while the stability of material structure can also be improved, and then is conducive to improve the chemical property of material.
Description
Technical field
The invention belongs to lithium ion battery technology and electrochemical fields, and in particular to a kind of metatitanic acid lithium cladding nickel cobalt manganese three
First positive electrode and preparation method thereof.
Background technique
Lithium ion battery is a kind of novel electrochmical power source, has specific energy height, power density height, has extended cycle life, certainly
It discharges the features such as small, cost performance is high, referred to as " environmentally protective power supply ".Lithium ion battery is not only in portable electrics such as mobile phones
It is used widely in sub- product, while there is also wide application prospects in electric automobiles.Fly in lithium ion battery
During speed development, positive electrode is to restrict its large-scale promotion and application or even the bottleneck to dominate the market, so in lithium
In the commercialized process of ion battery, most critical and with decisive role is that the excellent positive material of cost performance is made
Material.Positive electrode used at present has the materials such as cobalt acid lithium, LiMn2O4, LiFePO4, nickel cobalt manganese (NCA), nickel cobalt manganese (NCM).
Synthesize at this stage NCM most popular method be using coprecipitation, can according to experiment condition to the granularity of product,
Pattern etc. carries out regulation and equipment is simple, it is easy to operate.Coprecipitation is usually first by nickel salt, cobalt salt and manganese salt and complexing agent ammonia
Water, lye NaOH cocurrent are added to reaction kettle preparation divalent co-precipitation presoma, are then sintered with lithium.The material of this method preparation
There is reversible capacities it is low, high rate performance is poor the disadvantages of.
Carrying out coating modification to material at present is considered as the effective of raising anode material for lithium-ion batteries chemical property
Means.Firstly, coating modification can prevent active material and electrolyte contacts, inhibit the generation of side reaction, promotes positive electrode
Cycle performance；Secondly, high electrical conductivity materials such as carbon coating can increase positive electrode electronic conductivity, the multiplying power of material is promoted
Performance.
Summary of the invention
For the deficiency of nickel-cobalt-manganese ternary material, the invention proposes a kind of metatitanic acid lithiums to coat nickel-cobalt-manganese ternary anode material
Material and preparation method thereof, it is intended to metatitanic acid lithium clad anode material be promoted by addition chelating agent, to improve nickel-cobalt-manganese ternary material
Expect cycle performance and capacity retention ratio in lithium ion battery.
The present invention is to realize goal of the invention, is adopted the following technical scheme that
A kind of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material, it is characterized in that: it is with nickel-cobalt-manganternary ternary anode material
As kernel, metatitanic acid lithium is coated on the surface of the kernel；The general formula of the nickel-cobalt-manganternary ternary anode material is LiNi1-x- yCoxMnyO2, wherein 0 < x≤0.1,0 < y≤0.1；The metatitanic acid lithium is Li2TiO3。
Preferably, in metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material, the quality of metatitanic acid lithium accounts for 0.5%.
Metatitanic acid lithium metatitanic acid lithium cladding nickel of the present invention bores the preparation method of manganese tertiary cathode material, includes the following steps:
(1) nickel salt, cobalt salt and manganese salt is soluble in water, it is thoroughly mixed uniformly, obtains mixed solution；
(2) mixed solution that sodium hydroxide solution, ammonia spirit and step (1) obtain is added to four mouthfuls of burnings by peristaltic pump
In bottle, nickel cobalt manganese hydroxide precursor is obtained by coprecipitation reaction；
(3) after mixing by the nickel cobalt manganese hydroxide precursor and lithium source, in the tube furnace of logical oxygen with 2~
The heating rate of 5 DEG C/min is warming up to 450~500 DEG C, keeps the temperature 5h, then 750 are warming up to the heating rate of 2~5 DEG C/min~
850 DEG C, keep the temperature 15h；It is ground up, sieved after furnace cooling, obtains nickel cobalt manganese lithium oxide powder LiNi1-x-yCoxMnyO2, as nickel
Cobalt-manganese ternary positive electrode；
(4) titanium source, lithium source and chelating agent are weighed and is put into ultrasound in appropriate dehydrated alcohol, adds LiNi1-x-yCoxMnyO2Powder
End stirs evenly, and is subsequently poured into mortar and is ground to dehydrated alcohol and volatilizees completely, obtained solid powder is 650 in air atmosphere
DEG C heat preservation calcining 5h to get to metatitanic acid lithium coat nickel-cobalt-manganternary ternary anode material.
Preferably, the nickel salt, cobalt salt and manganese salt are one of sulfate, acetate and nitrate.
Preferably, in step (1) nickel salt, cobalt salt and manganese salt, the molar ratio of nickle atom, cobalt atom and manganese atom is 8:
1:1。
Preferably, in step (2): it is 11 ± 0.5 that pH value of solution is controlled during the coprecipitation reaction；The co-precipitation is anti-
Should be reacted for 24 hours with nitrogen as protection gas at 50 DEG C.
Preferably, the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium acetate.
Preferably, in step (3), the molar ratio of nickel cobalt manganese hydroxide precursor and lithium ion is 1:1.05.
Preferably, in step (4), the titanium source is at least one of titanium dioxide and butyl titanate, the chelating
Agent is EDTA, LAS (neopelex), in CTAB (cetyl trimethylammonium bromide) and PEG (polyethylene glycol)
It is at least one.
Preferably, in step (4), the molar ratio of titanium ion, lithium ion and chelating agent is 1:2:1.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, metatitanic acid lithium of the present invention coats nickel-cobalt-manganternary ternary anode material, is to make kernel with nickel-cobalt-manganternary ternary anode material,
Surface is coated with metatitanic acid lithium, spinel structure metatitanic acid lithium (Li2TiO3) crystal structure energy during lithium ion is embedded in deintercalation
The enough stability for keeping height, volume change very little, thus there is good cycle life, effectively prevent the formation of SEI film
It is deposited with lithium metal, and current potential rises rapidly at the end of charging, avoids overcharge, thus there is preferable safety.
Li2TiO3Cladding can not only improve the conductivity of lithium ion, while can also improve the stability of material structure, and then be conducive to mention
The chemical property of high material is effectively reduced erosion of the electrolyte to electrode material, inhibits the adverse reaction of positive electrode surface
Generation, possess higher Ion transfer ability and electron transmission ability, improve the cycle performance of nickelic ternary material.
2, the present invention adds chelating agent during cladding, by the coordination ability of chelating agent, promotes metal ion in material
Material surface more evenly closely combines, and uniform metatitanic acid lithium clad is generated after adding titanium source and lithium source, to inhibit
Side reaction between positive electrode and electrolyte effectively increases the chemical property of material.
Detailed description of the invention
Fig. 1 is the XRD diagram of the NCM positive electrode prepared under condition of different pH of the embodiment of the present invention 1；
Fig. 2 is the cycle performance figure of the NCM positive electrode prepared under condition of different pH of the embodiment of the present invention 1；
Fig. 3 is NCM prepared by the embodiment of the present invention 1 (pH=11) material, Li prepared by embodiment 22TiO3@NCM material
CATB+Li prepared by material, embodiment 32TiO3The XRD diagram of@NCM material；
Fig. 4 is NCM prepared by the embodiment of the present invention 1 (pH=11) material, Li prepared by embodiment 22TiO3@NCM material
CATB+Li prepared by material, embodiment 32TiO3The first circle charging and discharging curve figure of@NCM material；
Fig. 5 is NCM prepared by the embodiment of the present invention 1 (pH=11) material, Li prepared by embodiment 22TiO3@NCM material
CATB+Li prepared by material, embodiment 32TiO3The cycle performance figure of@NCM material.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
The preparation of embodiment 1, nickel-cobalt-manganternary ternary anode material
(1) according to the molar ratio of Ni:Co:Mn=80:10:10 weigh 10.674g nickel sulfate, 1.413g cobaltous sulfate,
0.854g manganese sulfate, adds water 100mL, and stirring and dissolving obtains the mixed solution of 100mL concentration 0.5mol/L.
(2) using four-hole boiling flask as reaction kettle, 100mL1mo/L ammonia spirit as bottom liquid, passing through peristaltic pump will
The mixed solution that the ammonia spirit of 1mol/L, the sodium hydroxide of 2mol/L and step (1) obtain is pumped into four-hole boiling flask.Keep four
The pH of solution is 10.5 in mouth flask, with nitrogen as protection gas, is aged for 24 hours in 50 DEG C of coprecipitation reactions, products therefrom filtering
Nickel cobalt manganese hydroxide precursor is made in washing and drying；
(3) 5g nickel cobalt manganese hydroxide precursor powder and 2.0415g lithium carbonate powder (lithiumation proportion is 1.05) is mixed
After closing uniformly, in the tube furnace of logical oxygen, 480 DEG C of heat preservation 5h are warming up to the heating rate of 2 DEG C/min, then with 2 DEG C/min
Heating rate be warming up to 800 DEG C of heat preservation 15h；It is ground up, sieved after furnace cooling, obtains NCM material powder
LiNi0.8Co0.1Mn0.1O2。
It is 11,11.5 that pH in step (2), which is adjusted separately, prepares NCM material by above-mentioned identical method.
Fig. 1 is the XRD diagram of the present embodiment NCM positive electrode prepared under condition of different pH, as can be seen from the figure
When pH=11, gained NCM positive electrode diffraction maximum is more sharp, better crystallinity degree.
Electrochemical property test is carried out to each sample obtained by the present embodiment: being conductive using NCM material as active material, SP
Agent, PVDF are binder, n-methyl-2-pyrrolidone (NMP) is dispersing agent, by the quality of NCM:SP:PVDF=80:10:10
Than sizing mixing, it is applied on aluminium foil and is made into positive plate.Then using metal lithium sheet as cathode, using microporous polypropylene membrane as diaphragm, with
The LiPF of 1mol/L6For electrolyte, CR2032 type battery is made in the glove box full of argon gas.
0.1c constant current charge-discharge test is carried out at normal temperature to each sample, charge and discharge blanking voltage is 2.8V-4.3V.Such as figure
Shown in 2, after tested: the first discharge specific capacity of NCM material (pH=10.5) is 143.47mAh/g, discharges and holds after 50 circle circulations
Amount is 102.69mAh/g, capacity retention ratio 71.57%；The first discharge specific capacity of NCM material (pH=11) is
179.91mAh/g, discharge capacity is 136.04mAh/g, capacity retention ratio 75.56% after 50 circles recycle；NCM material (pH=
11.5) first discharge specific capacity is 154.94mAh/g, and discharge capacity is 128.88mAh/g, capacity retention ratio after 50 circle circulations
It is 83.18%.As can be seen that in pH=11, the nickel-cobalt-manganternary ternary anode material charge-discharge performance and cycle performance of preparation compared with
It is good.
0.5c constant current charge-discharge test is carried out at normal temperature to the CR2032 type battery assembled by NCM material (pH=11),
Charge and discharge blanking voltage is 2.8V-4.3V.As shown in Figure 4,5, after tested: the material first discharge specific capacity is 143.36mAh/
G, discharge capacity is 113.50mAh/g, capacity retention ratio 79.17% after 100 circles recycle.
The preparation (no chelating agent) of embodiment 2, metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material
Weigh 0.01388gLi2CO3、0.0150gTiO2Ultrasonic, the addition preparation of 2g embodiment 1 is dissolved in 4mL dehydrated alcohol
NCM (pH=11) powder formed suspension, at room temperature magnetic agitation half an hour, then above-mentioned suspension is poured into mortar,
Dehydrated alcohol is ground at room temperature to volatilize completely；Obtained solid powder is placed in Muffle furnace, and 650 DEG C of heat preservations are forged in air atmosphere
5h is burnt, metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material Li is obtained after cooling2TiO3@NCM。
Electrochemical property test is carried out to each sample obtained by the present embodiment: with Li2TiO3@NCM material is active material, SP
For conductive agent, PVDF be binder, n-methyl-2-pyrrolidone (NMP) is dispersing agent, by Li2TiO3@NCM:SP:PVDF=
The mass ratio of 80:10:10 is sized mixing, and is applied on aluminium foil and is made into positive plate.Then using metal lithium sheet as cathode, with polypropylene microporous
Film is diaphragm, the LiPF with 1mol/L6For electrolyte, CR2032 type battery is made in the glove box full of argon gas.To sample
0.5c constant current charge-discharge test is carried out at normal temperature, and charge and discharge blanking voltage is 2.8V-4.3V.As shown in Figure 4,5, after tested:
The material first discharge specific capacity is 166.14mAh/g, and discharge capacity is 137.93mAh/g, capacity retention ratio after 100 circle circulations
It is 83.02%.
The preparation of embodiment 3, metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material (using CTAB as chelating agent)
Weigh 0.0337gCATB, 0.01388gLi2CO3、0.0150gTiO2Ultrasonic, addition implementation is dissolved in dehydrated alcohol
NCM (pH=11) powder prepared by example 1 forms suspension, at room temperature magnetic agitation half an hour, then pours into above-mentioned suspension
In mortar, it is ground to dehydrated alcohol at room temperature and volatilizees completely；Obtained solid powder is placed in Muffle furnace, 650 in air atmosphere
DEG C heat preservation calcining 5h, obtains metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material CATB+Li after cooling2TiO3@NCM。
Electrochemical property test is carried out to each sample obtained by the present embodiment: with CATB+Li2TiO3@NCM material is active matter
Matter, SP are conductive agent, PVDF is binder, n-methyl-2-pyrrolidone (NMP) is dispersing agent, by CATB+Li2TiO3@NCM:
The mass ratio of SP:PVDF=80:10:10 is sized mixing, and is applied on aluminium foil and is made into positive plate.Then using metal lithium sheet as cathode, with
Microporous polypropylene membrane is diaphragm, the LiPF with 1mol/L6For electrolyte, the production CR2032 type electricity in the glove box full of argon gas
Pond.0.5c constant current charge-discharge test is carried out at normal temperature to sample, charge and discharge blanking voltage is 2.8V-4.3V.Such as Fig. 4,5 institutes
Show, after tested: the material first discharge specific capacity is 172.17mAh/g, and discharge capacity is 142.99mAh/g after 100 circle circulations,
Capacity retention ratio is 83.05%.
By morphology characterization: NCM material prepared by the embodiment of the present invention is spherical in shape, and average grain diameter is about 10 μ
M, particle outline clear surface is without attachment.Its particle surface soft edge of the NCM sample of metatitanic acid lithium cladding is coarse and considerable
Observe the clad that average thickness is 8-10nm.The NCM material of chelating agent is added during cladding, clad distribution is more equal
It is even.In summary, suitable metatitanic acid lithium cladding can effectively improve discharge capacity for the first time and capacity retention ratio, and chelating agent adds
Adding keeps covered effect more preferable.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of metatitanic acid lithium coats nickel-cobalt-manganternary ternary anode material, it is characterised in that: made with nickel-cobalt-manganternary ternary anode material
For kernel, it is coated with metatitanic acid lithium on the surface of the kernel, the general formula of the nickel-cobalt-manganternary ternary anode material is LiNi1-x- yCoxMnyO2, wherein 0 < x≤0.1,0 < y≤0.1.
2. metatitanic acid lithium according to claim 1 coats nickel-cobalt-manganternary ternary anode material, it is characterised in that: in cladding process
Middle addition chelating agent is to promote to coat.
3. metatitanic acid lithium according to claim 1 or 2 coats nickel-cobalt-manganternary ternary anode material, it is characterised in that: described
Metatitanic acid lithium coats in nickel-cobalt-manganternary ternary anode material, and the quality of metatitanic acid lithium accounts for 0.5%.
4. the preparation method of a kind of claim 1,2 or the 3 metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode materials, feature exist
In including the following steps:
(1) nickel salt, cobalt salt and manganese salt is soluble in water, it is thoroughly mixed uniformly, obtains mixed solution；
(2) mixed solution that sodium hydroxide solution, ammonia spirit and step (1) obtain is added to four-hole boiling flask by peristaltic pump
In, nickel cobalt manganese hydroxide precursor is obtained by coprecipitation reaction；
(3) after mixing by the nickel cobalt manganese hydroxide precursor and lithium source, in the tube furnace of logical oxygen with 2~5 DEG C/
The heating rate of min is warming up to 450~500 DEG C, keeps the temperature 5h, then be warming up to 750~850 with the heating rate of 2~5 DEG C/min
DEG C, keep the temperature 15h；It is ground up, sieved after furnace cooling, obtains nickel cobalt manganese lithium oxide powder LiNi1-x-yCoxMnyO2, as nickel cobalt manganese
Tertiary cathode material；
(4) titanium source, lithium source and chelating agent are weighed and is put into ultrasound in appropriate dehydrated alcohol, adds LiNi1-x-yCoxMnyO2Powder,
It stirs evenly, is subsequently poured into mortar and is ground to dehydrated alcohol and volatilizees completely, obtained solid powder 650 DEG C of guarantors in air atmosphere
Temperature calcining 5h coats nickel-cobalt-manganternary ternary anode material to get to metatitanic acid lithium.
5. the preparation method of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 4, it is characterised in that:
In step (1), the nickel salt, cobalt salt and manganese salt are one of sulfate, acetate and nitrate.
6. the preparation method of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 4, it is characterised in that:
In step (1) nickel salt, cobalt salt and manganese salt, the molar ratio of nickle atom, cobalt atom and manganese atom is 8:1:1.
7. the preparation method of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 4, which is characterized in that
In step (2): it is 11 ± 0.5 that pH value of solution is controlled during the coprecipitation reaction；The coprecipitation reaction be with nitrogen as
Gas is protected, is reacted for 24 hours at 50 DEG C.
8. the preparation method of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 4, it is characterised in that:
The lithium source is at least one of lithium hydroxide, lithium carbonate and lithium acetate；The titanium source is titanium dioxide and butyl titanate
At least one of；The chelating agent is at least one of EDTA, LAS, CTAB and PEG.
9. the preparation method of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 4, it is characterised in that:
In step (3), the molar ratio of nickel cobalt manganese hydroxide precursor and lithium ion is 1:1.05.
10. the preparation method of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material according to claim 2, feature exist
In: in step (4), the molar ratio of titanium ion, lithium ion and chelating agent is 1:2:1.
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| CN112479267A (en) * | 2020-11-27 | 2021-03-12 | 广东邦普循环科技有限公司 | Ternary cathode material and preparation method and application thereof |
| CN113097460A (en) * | 2021-03-29 | 2021-07-09 | 清华大学 | Ternary cathode material @ indium oxide core-shell structure composite material and preparation method thereof |
| CN113097459A (en) * | 2021-03-29 | 2021-07-09 | 清华大学 | Ternary cathode material @ titanium nitride core-shell structure composite material and preparation method thereof |
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