CN109638232A - A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material - Google Patents
A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material Download PDFInfo
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- 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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of preparation methods of cladded type ternary cobalt nickel oxide manganses lithium anode material, comprising the following steps: (1) ternary nickel cobalt manganese lithium precursor preparation；(2) oxide cladded type ternary nickel cobalt manganese lithium precursor preparation；(3) prepared by ion conductor oxide cladded type ternary nickel cobalt manganese lithium anode material.The preparation method of positive electrode of the invention makes lithium ion be easier deintercalation in material surface, improves the high temperature cyclic performance of material；Clad is not reacted with electrolyte, is reduced contact of the material of main part with electrolyte and the generation of interface side reaction that causes, is improved the security performance of material；The processing performance in pole piece homogenate coating process is improved, the high temperature cyclic performance that material is assembled into after battery is improved；The positive electrode of preparation does not need to carry out double roasting technique, reduces energy consumption, has saved cost.
Description
Technical field
The invention belongs to electrode material of secondary lithium ion battery preparation fields, relate in particular to a kind of cladded type ternary oxygen
Change the preparation method of nickel cobalt manganese lithium anode material.
Background technique
To meet electric car and regenerative resource storage system demand, lithium ion battery (LIB) of new generation will have higher
Energy/power density, longer cycle life and better security performance.Positive electrode is the restricted ingredient of capacity.Make
For excellent layered lithium transition metal oxide high pressure LIBs positive electrode, ternary nickel cobalt manganese lithium (NCM) material and LiCoO2Phase
Than with many advantages, such as high specific capacity, low cost, hypotoxicity and preferable security performance.But NCM material is still
There is a problem of that a serious i.e. high temperature cyclic performance is bad, the NCM material capacity drop that declines greatly accelerates at high temperature, seriously affects
The service life of lithium ion battery.
The Liu et al. people of Fudan University in Shanghai carries out deep grind for the mechanism of NCM622 material high temperature circulation at 55 DEG C
Study carefully (Journal of Power Sources, 2018,393,92~98).Research shows that NCM622 material is in high temperature and high voltage
Serious mixing phenomenon can occur for the metal cation on its surface layer during circulation, and charge-exchange impedance is caused to dramatically increase.
Furthermore high temperature and high voltage cycle can also aggravate LiPF6In the decomposition of electrode surface, increase LiF and NiF2Content, cause electricity
Pole/electrolyte interface impedance increase.The reason of two aspects cause high temperature circulation to deteriorate is directed to the surface chemical reaction of material.
In order to improve the high temperature circulation of material it is necessary to setting about the stability for promoting material from material surface；Metal oxidation
Object or nonmetal oxide cladding are a kind of common methods, and surface coats one layer of metal oxide or nonmetal oxide type is blunt
The dissolution of metallic element in the electrolytic solution in material can be reduced with the direct contact of inhibitory activity material and electrolyte by changing film, together
When have document report (Angew.Chem.Int.Ed.2015,54,4440~4458) cladding can reduce coating metal cation
Mixing phenomenon and irreversible transition caused by structural instability.
Currently, industrially generalling use Al2O3Or SiO2Liquid phase or solid phase coat ternary NCM material.But above-mentioned clad material
Material belongs to block type inertia covering material, and electronic conductivity and ionic conductivity are lower, are not ideal clad
Material cannot effectively improve the high temperature cyclic performance of material.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of cladded type ternary cobalt nickel oxide manganses lithium anode material, can
The ionic conductivity for improving positive electrode, to promote the high temperature cyclic performance and security and stability of material.
The present invention is achieved by the following technical solutions:
A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material, comprising the following steps:
(1) ternary nickel cobalt manganese lithium precursor preparation:
N is passed through into reaction kettle2, dilute ammoniacal liquor is added as bottom liquid, by coprecipitation method according to Ni by peristaltic pump:
Co:Mn=(50~60): (15~20): respectively reaction kettle is added in the aqueous solution of nickel salt, cobalt salt and manganese salt by 30 molar ratio, together
When, it is separately added into sig water and concentrated ammonia liquor, 15~30h of reaction is continuously stirred at a temperature of 45~60 DEG C and controls reaction system
PH=10.5~11.5；The precipitating that reaction generates is filtered, washed, dries, and obtains ternary nickel cobalt manganese lithium presoma；
(2) oxide cladded type ternary nickel cobalt manganese lithium precursor preparation:
The alcoholic solution I that covering material-dissolution is formed to covering material in alcoholic solvent, by the ternary nickel cobalt manganese lithium forerunner
Body is added dispersion a period of time in alcoholic solvent and forms suspension II, after the alcoholic solution I of the covering material is added it is described suspended
In liquid II, stirring 2-15h sufficiently carries out mixing cladding, forms suspension III, finally that a certain proportion of alcohol-water mixture is slow
Be added dropwise in the suspension III, hydrolyze covering material, continue stirring so that hydrolysis is continued 20-25h after, be centrifuged, wash
It washs, it is dry, obtain oxide cladded type ternary nickel cobalt manganese lithium presoma；
(3) prepared by ion conductor oxide cladded type ternary nickel cobalt manganese lithium anode material:
Above-mentioned oxide cladded type ternary nickel cobalt manganese lithium presoma is done with lithium carbonate or lithium hydroxide with certain mol proportion
Method or wet-mixing are uniform, obtain cladded type ternary cobalt nickel oxide manganses lithium anode material in the calcining of air atmosphere roller way kiln, crushing
Material；
Nickel salt described in above-mentioned step (1), cobalt salt, manganese salt the concentration of aqueous solution be 2mol/L.The nickel salt, cobalt
Salt, manganese salt are the sulfate, chlorate or nitrate for being dissolved in water.
The concentration of dilute ammoniacal liquor described in above-mentioned step (1) is 0.5~2mol/L.The additional amount of dilute ammoniacal liquor is reaction
The 1/4~1/2 of effective volume inside kettle.
In above-mentioned step (1), the sig water, metal salt solution (MSO4) and concentrated ammonia liquor additional amount according to alkali: gold
Belong to salt: NH3·H2The molar ratio of O is (1.4~2.5): (1~1.5): 1 is added.Wherein, the sig water concentration is 4~5mol/
L；The concentration of the concentrated ammonia liquor is 20%~22wt% (11.5M~12.5M).Preferably, the sig water is NaOH solution,
Metal salt solution is the sulfate liquor of nickel, cobalt, manganese.
Preferably, alcoholic solvent described in step (2) is ethyl alcohol or propyl alcohol；The covering material is Organometallic compounds
Object, preferably Zr, Nb, Ti or other can be dissolved in high-valence state (+3~+5 valence) metal compound that alcoholic solution is formed in alcoholic solvent
Object, preferred covering material are butanol zirconium, n-butanol niobium or butyl titanate (n-butanol phthalein).
Preferably, in step (2) described alcohol-water mixture, the volume ratio of deionized water and alcoholic solvent is 1/10~1/
15；The molar content of nickel is 50%~60% in the ternary cobalt nickel oxide manganses lithium presoma or positive electrode.
Preferably, the lithium carbonate in step (3), lithium hydroxide preferred battery grade；The oxide cladded type nickel ternary
It is (1.0~1.12) that cobalt manganese lithium presoma and lithium source, which press lithium ion and the molar ratio of metal ion total amount: 1；Using dry mixed
When, preferred high-speed mixer；It when using wet-mixing, is mixed in alcoholic solvent, is dried after mixing.Preferably,
The calcination temperature is 700~1000 DEG C, and calcination time is 10~30 hours.
The preparation method of positive electrode of the invention first aoxidizes nickel cobalt manganese lithium presoma using liquid phase coating method
Object homogeneously coats, and then by mixing, calcining with lithium source, prepares a kind of ion conductor oxide cladding on positive electrode surface
Layer.
The invention has the following advantages:
1, the ion that the ion conductor type oxide cladding layers formed in method of the invention can be improved positive electrode passes
The property led, so that lithium ion is easier deintercalation in material surface, so as to promote the high temperature cyclic performance of material；Clad simultaneously
It is not reacted with electrolyte, thus reduce contact of the material of main part with electrolyte and the generation of interface side reaction that causes, so as to
To promote the security performance of material.
2, the present invention uses liquid phase coating method, improves the uniformity of material cladding, compares solid powder, suspension or cream
The alcoholic solution of turbid covering material, metal can preferably infiltrate, wrap up presoma；Uniform clad is also that material at high temperature follows
The factor that ring performance and security performance are promoted；
3, using oxide liquid form method for coating, the remaining alkali content on nickel cobalt manganese lithium anode material surface is reduced,
The processing performance in pole piece homogenate coating process is improved, so as to promote the high temperature circulation after material is assembled into battery
Energy；
4, due to carrying out liquid phase coating, the nickel cobalt manganese lithium anode material produced using method of the invention to presoma
It does not need progress double roasting technique and has saved cost to reduce energy consumption.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material, comprising the following steps:
(1) ternary nickel cobalt manganese lithium precursor preparation:
1) metal salt solution is prepared: adding water to be configured to respectively 6 hydration nickel sulfates, 7 cobalt sulfate hydrates, 1 hydrated manganese sulfate
The salting liquid of 2mol/L；
2) sig water is prepared: 30% concentrated sodium hydroxide lye (about 10.7M) is diluted to the sig water of 4mol/L；
3) dilute ammoniacal liquor is prepared: 22% concentrated ammonia liquor (about 12.5M) is diluted with water to the dilute ammoniacal liquor for being configured to 2mol/L.
N is passed through into 10L reaction kettle2, dilute ammoniacal liquor 5L of 2mol/L is first added by peristaltic pump as bottom liquid, by coprecipitated
Shallow lake method respectively adds above-mentioned nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution according to the molar ratio of Ni:Co:Mn=5:2:3
Enter reaction kettle, while being separately added into above-mentioned sig water and concentrated ammonia liquor, wherein sodium hydroxide sig water (NaOH), metal salt solution
(MSO4), concentrated ammonia solution (NH3, aq.) be added ratio according to NaOH:MSO4: NH3·H2O. molar ratio is 2:1:1 addition；
Reaction 15h is continuously stirred at 50 DEG C；Online pH meter monitors pH=11；The precipitating that reaction generates is filtered, washed, dries,
Obtain ternary nickel cobalt manganese lithium presoma.
(2) oxide cladded type ternary nickel cobalt manganese lithium precursor preparation:
Zirconium-n-butylate is dissolved to the ethanol solution I to form zirconium-n-butylate in ethanol, ternary nickel cobalt manganese lithium presoma is added
Entering in ethyl alcohol dispersion a period of time forms suspension II, after the ethanol solution I of zirconium-n-butylate is added in suspension II and stir 2h
It sufficiently carries out mixing cladding and forms suspension III, the alcohol-water mixture for being finally 1:10 by deionized water and the volume ratio of ethyl alcohol
Be slowly added dropwise in suspension III, hydrolyze zirconium-n-butylate, continue stirring continue hydrolysis for 24 hours after, centrifugation, washing,
Obtain zirconium oxide cladded type ternary nickel cobalt manganese lithium presoma；
(3) prepared by ion conductor oxide cladded type ternary nickel cobalt manganese lithium anode material:
By above-mentioned oxide cladded type ternary nickel cobalt manganese lithium presoma and lithium carbonate by lithium ion and metal ion total amount
Molar ratio is that 1.05:1 high-speed mixer dry mixed is uniform, small in 700 DEG C of calcinings 25 in roller way kiln under air atmosphere
When, it crushes later, obtains cladded type ternary cobalt nickel oxide manganses lithium nickel cobalt manganese lithium anode material；
Embodiment 2
A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material, comprising the following steps:
(1) ternary nickel cobalt manganese lithium precursor preparation:
1) metal salt solution is prepared: adding water to be configured to 2mol/ 6 hydration nickel sulfates, 7 cobalt sulfate hydrates, 1 hydrated manganese sulfate
The salting liquid of L；
2) sig water is prepared: 30% concentrated sodium hydroxide lye is diluted to the sig water of 4mol/L；
3) dilute ammoniacal liquor is prepared: 20% concentrated ammonia liquor is diluted with water to the dilute ammoniacal liquor for being configured to 0.5mol/L；
N will be passed through in 10L reaction kettle2, the dilute ammoniacal liquor 2.5L of 0.5mol/L is first added by peristaltic pump as bottom liquid, by altogether
According to the molar ratio of Ni:Co:Mn=5:2:3 reaction is added respectively in nickel salt solution, cobalt salt solution, manganese salt solution by intermediate processing
Kettle, while being separately added into sig water and concentrated ammonia liquor；Sodium hydroxide sig water (NaOH), metal salt solution (MSO4), concentrated ammonia liquor it is molten
Liquid (NH3, aq.) be added ratio according to molar ratio be 1.4:1.4:1；Reaction 20h is continuously stirred at 50 °C；Online pH meter
Monitor pH=11；The precipitating that reaction generates is filtered, washed, dries, and obtains ternary nickel cobalt manganese lithium presoma；
(2) oxide cladded type ternary nickel cobalt manganese lithium precursor preparation:
N-butanol niobium is diluted to the propanol solution I to form n-butanol niobium in propyl alcohol, ternary nickel cobalt manganese lithium presoma is added
Entering in propyl alcohol dispersion a period of time forms suspension II, after stirring 10h in suspension II be added in solution I sufficiently carry out mixing packet
It covers to form suspension III, finally by deionized water: propyl alcohol volume ratio is that the alcohol-water mixture of 1:15 is slowly added dropwise suspension
Make in III n-butanol niobium hydrolyze, continue stirring so that hydrolysis is continued 20h after, centrifugation, washing, zirconium oxide cladded type can be obtained
Ternary nickel cobalt manganese lithium presoma；
(3) prepared by ion conductor oxide cladded type ternary nickel cobalt manganese lithium anode material:
By above-mentioned oxide cladded type ternary nickel cobalt manganese lithium presoma and lithium carbonate by lithium ion and metal ion total amount
Molar ratio is that 1.05:1 high-speed mixer dry mixed is uniform, calcines 910 DEG C, 20 hours, rear powder in air atmosphere roller way kiln
It is broken to obtain cladded type ternary cobalt nickel oxide manganses lithium nickel cobalt manganese lithium anode material；
Embodiment 3
A kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material, comprising the following steps:
(1) ternary nickel cobalt manganese lithium precursor preparation:
1) metal salt solution is prepared: adding water to be configured to 2mol/ 6 hydration nickel sulfates, 7 cobalt sulfate hydrates, 1 hydrated manganese sulfate
The salting liquid of L；
2) sig water is prepared: 30% concentrated sodium hydroxide lye is diluted to the sig water of 5mol/L；
3) dilute ammoniacal liquor is prepared: 22% concentrated ammonia liquor is diluted with water to the dilute ammoniacal liquor for being configured to 1mol/L；
N will be passed through in 10L reaction kettle2, the dilute ammoniacal liquor 3.5L of 1mol/L is first added by peristaltic pump as bottom liquid, by coprecipitated
According to the molar ratio of Ni:Co:Mn=55:15:30 reaction is added respectively in nickel salt solution, cobalt salt solution, manganese salt solution by shallow lake method
Kettle, while being separately added into sig water and concentrated ammonia liquor；Sodium hydroxide sig water (NaOH), metal salt solution (MSO4), concentrated ammonia liquor it is molten
Liquid (NH3, aq.) be added ratio according to molar ratio be 2.5:1.5:1；Reaction 25h is continuously stirred at 50 °C；Online pH meter
Monitor pH=11；The precipitating that reaction generates is filtered, washed, dries, and obtains ternary nickel cobalt manganese lithium presoma；
(2) oxide cladded type ternary nickel cobalt manganese lithium precursor preparation:
N-butyl titanium is diluted to the ethanol solution I to form n-butyl titanium in ethanol, ternary nickel cobalt manganese lithium presoma is added
Entering in ethyl alcohol dispersion a period of time forms suspension II, after stirring 15h in suspension II be added in solution I sufficiently carry out mixing packet
It covers to form suspension III, finally by deionized water: ethyl alcohol volume ratio is that the alcohol-water mixture of 1:10 is slowly added dropwise suspension
Hydrolyze n-butyl titanium in III, continue stirring so that hydrolysis is continued 25h after, centrifugation, washing, titanium-oxide-coated type can be obtained
Ternary nickel cobalt manganese lithium presoma；
(3) prepared by ion conductor oxide cladded type ternary nickel cobalt manganese lithium anode material:
By above-mentioned oxide cladded type ternary nickel cobalt manganese lithium presoma and lithium carbonate by lithium ion and metal ion total amount
Molar ratio is that 1.05:1 high-speed mixer dry mixed is uniform, calcines 1000 DEG C, 18 hours, rear powder in air atmosphere roller way kiln
It is broken to obtain cladded type ternary cobalt nickel oxide manganses lithium anode material.
Performance test
The cladded type ternary cobalt nickel oxide manganses lithium anode material made from the method for the present invention in the various embodiments described above is made
2032 type button cells are simultaneously tested, and charge and discharge blanking voltage is 3.0~4.3V, and obtained electrochemical performance data is seen below
Table:
The above experimental data shows the cladded type ternary cobalt nickel oxide manganses lithium anode material system made from method of the invention
At button cell, first discharge specific capacity is greater than 165mAh/g, compared to the ternary nickel cobalt manganese lithium material of existing market commercialization,
Coulombic efficiency for the first time of the invention, which improves 3~6%, 2.0C multiplying power discharging specific capacity, can achieve the 88% of 0.1C specific discharge capacity
More than, the high temperature circulation of 50 weeks batteries remains to reach 97% or more capacity retention ratio, shows good chemical property.
Claims (10)
1. a kind of preparation method of cladded type ternary cobalt nickel oxide manganses lithium anode material, which comprises the following steps:
(1) ternary nickel cobalt manganese lithium precursor preparation:
N is passed through into reaction kettle2, dilute ammoniacal liquor is added as bottom liquid, by coprecipitation method according to Ni:Co:Mn=by peristaltic pump
(50~60): (15~20): respectively reaction kettle is added in the aqueous solution of nickel salt, cobalt salt and manganese salt by 30 molar ratio, meanwhile, respectively
Sig water and concentrated ammonia liquor is added, continuously stirs 15~30h of reaction at a temperature of 45~60 DEG C and controls the pH=of reaction system
10.5~11.5；The precipitating that reaction generates is filtered, washed, dries, and obtains ternary nickel cobalt manganese lithium presoma；
(2) oxide cladded type ternary nickel cobalt manganese lithium precursor preparation:
The alcoholic solution I that covering material-dissolution is formed to covering material in alcoholic solvent adds the ternary nickel cobalt manganese lithium presoma
Entering in alcoholic solvent dispersion a period of time forms suspension II, after the suspension II is added in the alcoholic solution I of the covering material
In, stirring 2-15h sufficiently carries out mixing cladding, forms suspension III, slowly dropwise by a certain proportion of alcohol-water mixture finally
Be added in the suspension III, hydrolyze covering material, continue stirring so that hydrolysis is continued 20-25h after, centrifugation, washing,
It is dry, obtain oxide cladded type ternary nickel cobalt manganese lithium presoma.
(3) prepared by ion conductor oxide cladded type ternary nickel cobalt manganese lithium anode material:
By above-mentioned oxide cladded type ternary nickel cobalt manganese lithium presoma and lithium carbonate or lithium hydroxide with certain mol proportion dry method or
Wet-mixing is uniform, obtains cladded type ternary cobalt nickel oxide manganses lithium anode material in the calcining of air atmosphere roller way kiln, crushing.
2. preparation method according to claim 1, it is characterised in that: nickel salt described in step (1), cobalt salt, manganese salt water
The concentration of solution is 2mol/L.
3. preparation method according to claim 2, it is characterised in that: the nickel salt, cobalt salt, manganese salt are the sulfuric acid for being dissolved in water
Salt, chlorate or nitrate.
4. preparation method according to claim 1, it is characterised in that: the concentration of dilute ammoniacal liquor described in step (1) be 0.5~
2mol/L。
5. the preparation method according to claim 4, it is characterised in that: the additional amount of dilute ammoniacal liquor is to have inside reaction kettle
Imitate the 1/4~1/2 of volume.
6. preparation method according to claim 1, it is characterised in that: in step (1), the sig water, metal salt solution
Additional amount with concentrated ammonia liquor is according to alkali: metal salt: NH3·H2The molar ratio of O is (1.4~2.5): (1~1.5): 1 is added.
7. preparation method according to claim 1, it is characterised in that: the concentration of sig water described in step (1) be 4~
5mol/L；The concentration of the concentrated ammonia liquor is 20~22wt%.
8. preparation method according to claim 1, it is characterised in that: alcoholic solvent described in step (2) is ethyl alcohol or third
Alcohol；The covering material is organo-metallic compound, and preferably it is molten can be dissolved in formation alcohol in alcoholic solvent by Zr, Nb, Ti or other
The high-valence state metallic compound of liquid, preferred covering material are zirconium-n-butylate, n-butanol niobium or n-butyl titanium.
9. preparation method according to claim 1, it is characterised in that: in alcohol-water mixture described in step (2), deionization
The volume ratio of water and alcoholic solvent is 1/10~1/15；The ternary cobalt nickel oxide manganses lithium presoma or ternary nickel cobalt manganese lithium anode material
The molar content of nickel is 50%~60% in material.
10. preparation method according to claim 1, it is characterised in that: before the oxide cladded type ternary nickel cobalt manganese lithium
It is (1.0~1.12) that body and lithium source, which are driven, by the molar ratio of lithium ion and metal ion total amount: 1；When using dry mixed, select high
Fast mixing machine；It when using wet-mixing, is mixed in alcoholic solvent, is dried after mixing；The calcination temperature be 700~
1000 DEG C, calcination time is 10~30 hours.
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