CN109585812A - A kind of lithium cobalt positive polar material and its preparation method and application - Google Patents
A kind of lithium cobalt positive polar material and its preparation method and application Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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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- H01M4/02—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention discloses a kind of lithium cobalt positive polar materials and its preparation method and application.This lithium cobalt positive polar material, including substrate and the clad for accounting for substrate mass percentage 0.05%~10%；The chemical formula of substrate is Li1+yCo1‑xAxO2；The chemical formula of clad is LiMaM’bM”cO2.It also discloses the preparation method of this lithium cobalt positive polar material simultaneously, also discloses application of this lithium cobalt positive polar material in lithium battery.A kind of new structural lithium cobalt positive polar material is prepared by wet chemical method in the present invention, and obtained material is evenly coated, and can improve the electrical property of positive electrode.
Description
Technical field
The present invention relates to a kind of lithium cobalt positive polar materials and its preparation method and application, belong to lithium battery technology
Field.
Background technique
Stratiform cobalt acid lithium is the current widest positive electrode of lithium ion battery commercial applications, the especially field 3C.Number
Decoding apparatus tends to lightening design, this is badly in need of the positive electrode of high-energy density.Presently mainly by improve compacted density and
Voltage is improved to improve the energy density of material.
The theoretical capacity of stratiform cobalt acid lithium is 274mAhg-1, operating voltage is generally 3.0~4.2V, and actual capacity is only
135-150mAh·g-1, the only 50-55% of theoretical capacity.However operating voltage is improved, with Li+Abjection, LixCoO2It can send out
Raw series of phase transitions process, leads to lattice parameter variation, lattice defect, displacement etc.；Cobalt acid lithium structural instability under high voltage, Li+Abjection will appear Co dissolution simultaneously, discharge oxygen and a series of side reactions occur with electrolyte.A series of this side reaction meeting
Reduce the specific discharge capacity and cyclical stability of cobalt acid lithium.
Cobalt acid lithium there are aiming at the problem that, related work person has done the high voltage that a large amount of study on the modification improve cobalt acid lithiums
Can, such as use new synthesis technology (sol-gal process, microwave method), doping vario-property (Mg, Al, Ti, Zr etc.), coating modification
(Al2O3、TiO2、AlPO4Deng).Usual method for coating is, by cobalt acid lithium substrate and cladding raw metal oxide or metal pentafluoride
Object dry mixed is uniform, cobalt acid lithium material after being coated using sintering.It is this method simple process, easy to operate but also difficult
To obtain uniform clad, to influence the electrical property of material.
Summary of the invention
It is an object of the present invention to overcoming the deficiencies of the prior art and provide the novel lithium cobalt composite oxide of one kind just
Pole material；The second object of the present invention is to provide the preparation method of this lithium cobalt positive polar material；Of the invention
The third purpose is to provide application of this lithium cobalt positive polar material in lithium battery.
The technical solution used in the present invention is:
A kind of lithium cobalt positive polar material, including substrate and the packet for accounting for substrate mass percentage 0.05%~10%
Coating；
The chemical formula of substrate is Li1+yCo1-xAxO2；The chemical formula of clad is LiMaM’bM”cO2；
In the chemical formula of substrate, one of A Mg, Al, Ti, Zr, Ni, Mn, Y, V, Mo, W or a variety of；0.001≤x≤
0.1,0≤y≤0.03；
In the chemical formula of clad, M, M ' and M " be respectively selected from any three kinds in Ni, Co, Mn, Al；0 < a < 1,0 <b < 1,
0 < c < 1, and a+b+c=1.
Preferably, in the chemical formula of this lithium cobalt positive polar material substrate, in A Mg, Al, Ti, Y at least
Two kinds；0.001≤x≤0.1,0≤y≤0.002.
Preferably, in the chemical formula of this lithium cobalt positive polar material clad, M Ni, M ' are Co, and M " is
Mn；1/3≤a≤0.8,0.1≤b≤1/3,0 < c≤1/3, and a+b+c=1.
The preparation method of this lithium cobalt positive polar material, comprising the following steps:
1) cobalt source, lithium source, doping metals source are uniformly mixed, obtain primary mixture；
2) primary mixture is sintered, obtains doping cobalt acid lithium substrate；
3) lithium source solution, doping cobalt acid lithium substrate, mixed metal solution, oxidant and aqueous slkali is anti-in a kettle
It answers, obtains slurry, slurry is dried to obtain secondary mixture；
4) secondary mixture is sintered, obtains lithium cobalt positive polar material.
Preferably, in the preparation method step 1) of this lithium cobalt positive polar material, cobalt source be cobaltosic oxide,
At least one of cobalt oxide, cobalt carbonate, cobalt acetate；It is further preferred that cobalt source is cobaltosic oxide.
Preferably, in the preparation method step 1) of this lithium cobalt positive polar material, lithium source is lithium carbonate, nitric acid
At least one of lithium, lithium hydroxide, lithia, lithium oxalate, lithium acetate；It is further preferred that lithium source is carbonic acid in step 1)
Lithium.
Preferably, in the preparation method step 1) of this lithium cobalt positive polar material, doping metals source is substrate
Li1+yCo1-xAxO2At least one of the oxide of middle element A, hydroxide, metal salt；It is further preferred that in step 1),
Doping metals source is at least one of oxide or hydroxide of Mg, Al, Ti, Zr, Ni, Mn, Y, V, Mo, W；Further
Preferably, doping metals source is at least one of oxide or hydroxide of Mg, Al, Ti, Y.
Preferably, in certain specific embodiments of the invention, preparation method step 1) is by cobalt source, lithium source and doping
Metal oxide is uniformly mixed, and obtains primary mixture；It is further preferred that in preparation method step 1), doping metals oxidation
Object is at least two in the oxide of Mg, Al, Ti, Y；Still further preferably, blended metal oxide is magnesia, three oxygen
Change two aluminium, titanium dioxide, at least two in yttrium oxide.
Preferably, in the preparation method step 1) of this lithium cobalt positive polar material, the metal in doping metals source
Element group becomes aforementioned substrates chemical formula Li1+yCo1-xAxO2In composition.
Preferably, in the preparation method step 2) of this lithium cobalt positive polar material, sintering is specially in air
In atmosphere, 8h~22h is sintered at 800 DEG C~1060 DEG C；It is further preferred that the sintering of step 2) is specially in air atmosphere
In, 10h~20h is sintered at 1000 DEG C~1060 DEG C.
Preferably, in the preparation method step 2) of this lithium cobalt positive polar material, the doping that is obtained after sintering
Cobalt acid lithium substrate is again through pulverization process.
Further, in the preparation method step 2) of this lithium cobalt positive polar material, resulting doping is prepared
The chemical formula of cobalt acid lithium substrate is Li above-mentioned1+yCo1-xAxO2。
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, first by lithium source solution with mix
Miscellaneous cobalt acid lithium substrate mixes in a kettle, then with mixed metal solution, oxidant and aqueous slkali hybrid reaction；Further preferably
, it is first 10min~30min with the time that doping cobalt acid lithium substrate mixes in a kettle by lithium source solution.
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, lithium source is lithium carbonate, nitric acid
At least one of lithium, lithium hydroxide, lithia, lithium oxalate, lithium acetate；Lithium source solution is respectively Lithium carbonate solution, nitric acid
Lithium solution, lithium hydroxide solution, lithia solution, lithium oxalate solution or lithium acetate solution；It is further preferred that in step 3)
Lithium source solution is lithium hydroxide solution.
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, mixed metal solution be by
LiMaM’bM”cO2Metal M, M of composition ', the respective acetate of M ", carbonate, sulfate, oxalates, chlorate, chlorate,
The mixed solution of bicarbonate composition；It is further preferred that mixed metal solution is metal M, M ', M " respective oxalates composition
Mixed solution；Still further preferably, mixed metal solution is that the mixing of the respective oxalates composition of Ni, Co, Mn, Al is molten
Liquid.
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, oxidant H2O2、
NaClO、KClO3、KMnO4At least one of；It is further preferred that oxidant is H2O2, one or both of NaClO.
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, alkali is alkali metal hydroxide
Object；It is further preferred that alkali is one or both of sodium hydroxide, potassium hydroxide；Aqueous slkali, that is, sodium hydroxide or hydroxide
The aqueous solution of potassium.
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, the temperature of reaction is 40 DEG C
~150 DEG C, the time of reaction is 10h~48h, and the pH of reaction is 9~13；It is further preferred that in step 3), the temperature of reaction
It is 80 DEG C~120 DEG C, the time of reaction is 10h~20h.
Preferably, in the preparation method step 3) of this lithium cobalt positive polar material, the stirring rate of reaction kettle
For 200r/min~600r/min.
Preferably, in the preparation method step 4) of this lithium cobalt positive polar material, sintering is specially in air
In atmosphere, 5h~for 24 hours is sintered at 400 DEG C~1000 DEG C；It is further preferred that sintering is specially in air atmosphere in step 4)
In, 5h~10h is sintered at 900 DEG C~1000 DEG C.
A kind of lithium battery, lithium cobalt positive polar material just extremely above-mentioned.
The beneficial effects of the present invention are:
A kind of new structural lithium cobalt positive polar material is prepared by wet chemical method in the present invention, made
The material obtained is evenly coated, and the cycle performance of material can be improved.
Detailed description of the invention
Fig. 1 is the XRD diagram of lithium cobalt positive polar material in embodiment 1；
Fig. 2 is the SEM figure of lithium cobalt positive polar material in embodiment 1；
Fig. 3 is the SEM figure of lithium cobalt positive polar material in comparative example 1；
Fig. 4 is the cycle performance figure of embodiment and comparative example lithium cobalt positive polar material.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1
The lithium cobalt positive polar material of embodiment 1, substrate Li1.001Co0.995Mg0.002Al0.003O2, clad
For the LiNi for accounting for substrate mass 0.1%1/3Co1/3Mn1/3O2。
1 lithium cobalt positive polar material of embodiment the preparation method comprises the following steps:
(1) 2000g cobaltosic oxide, 960g lithium carbonate, 2g magnesia, 3.8g aluminum oxide are weighed, is uniformly mixed, obtains
To uniform mixture；
(2) mixture obtained by step (1) is sintered 16h at air atmosphere, 1040 DEG C, by crushing after natural cooling,
Obtain the doping cobalt acid lithium substrate that partial size is 13-22 μm；
(3) it presses clad composition and prepares mixed metal oxalate solution, concentration is 0.042mol/L (by rubbing for Ni:Co:Mn
You are than being that 1:1:1 is prepared, i.e. the concentration of Ni, Co, Mn are respectively 0.014mol/L, and the method for the following example 2-5 is similar)；
NaOH solution, concentration 0.42mol/L；The lithium hydroxide solution of 0.42mol/L is added in reaction kettle, then by the step of 2kg
Suddenly cobalt acid lithium substrate obtained by (2) is added thereto, and stirs 30min；Mixed metal solution, H2O2It is added and reacts with NaOH solution cocurrent
In kettle.It is 12~13 that pH is controlled in reaction process, mixing speed 400r/min, and temperature of reaction kettle is 90 DEG C.React 20h filtering
After obtain slurry, as secondary mixture；
(4) secondary mixture obtained by step (3) is sintered 10h at 1000 DEG C, obtains lithium cobalt positive polar material
Material.
Embodiment 2
The lithium cobalt positive polar material of embodiment 2, substrate Li1.001Co0.995Mg0.002Al0.002Ti0.001O2, packet
Coating is the LiNi for accounting for substrate mass 0.1%0.5Co0.2Mn0.3O2。
2 lithium cobalt positive polar material of embodiment the preparation method comprises the following steps:
(1) 2000g cobaltosic oxide, 960g lithium carbonate, 2g magnesia, 2.5g aluminum oxide, 2g titanium dioxide are weighed,
It is uniformly mixed, obtains uniform mixture；
(2) mixture obtained by step (1) is sintered 16h at air atmosphere, 1040 DEG C, by crushing after natural cooling,
Obtain the doping cobalt acid lithium substrate that partial size is 13-22 μm；
(3) it presses clad composition and prepares mixed metal oxalate solution, concentration 0.042mol/L；NaOH solution, concentration
For 0.42mol/L；The lithium hydroxide solution of 0.42mol/L is added in reaction kettle, then by the acid of cobalt obtained by (2) the step of 2kg
Lithium substrate is added thereto, and stirs 30min；Mixed metal solution, NaClO and NaOH solution cocurrent are added in reaction kettle.It reacted
It is 12~13 that pH is controlled in journey, mixing speed 400r/min, and temperature of reaction kettle is 100 DEG C.It is starched after reaction 20h filtering
Material, as secondary mixture；
(4) secondary mixture obtained by step (3) is sintered 10h at 1000 DEG C, obtains lithium cobalt positive polar material
Material.
Embodiment 3
The lithium cobalt positive polar material of embodiment 3, substrate Li1.001Co0.995Mg0.002Al0.003O2, clad
For the LiNi for accounting for substrate mass 0.3%1/3Co1/3Mn1/3O2。
3 lithium cobalt positive polar material of embodiment the preparation method comprises the following steps:
(1) 2000g cobaltosic oxide, 960g lithium carbonate, 2g magnesia, 3.8g aluminum oxide are weighed, is uniformly mixed, obtains
To uniform mixture；
(2) mixture obtained by step (1) is sintered 16h at air atmosphere, 1030 DEG C, by crushing after natural cooling,
Obtain the doping cobalt acid lithium substrate that partial size is 13-22 μm；
(3) it presses clad composition and prepares mixed metal oxalate solution, concentration 0.126mol/L；NaOH solution, concentration
For 1.26mol/L；The lithium hydroxide solution of 1.26mol/L is added in reaction kettle, then by the acid of cobalt obtained by (2) the step of 2kg
Lithium substrate is added thereto, and stirs 30min；Mixed metal solution, H2O2It is added in reaction kettle with NaOH solution cocurrent.Reaction process
Middle control pH is 12~13, mixing speed 400r/min, and temperature of reaction kettle is 90 DEG C.Slurry is obtained after reaction 20h filtering, i.e.,
For secondary mixture；
(4) secondary mixture obtained by step (3) is sintered 10h at 1000 DEG C, obtains lithium cobalt positive polar material
Material.
Embodiment 4
The lithium cobalt positive polar material of embodiment 4, substrate Li1.001Co0.996Y0.002Al0.002O2, clad is
Account for the LiNi of substrate mass 0.1%1/3Co1/3Mn1/3O2。
4 lithium cobalt positive polar material of embodiment the preparation method comprises the following steps:
(1) 2000g cobaltosic oxide, 960g lithium carbonate, 5.6g yttrium oxide, 2.5g aluminum oxide are weighed, is uniformly mixed,
Obtain uniform mixture；
(2) mixture obtained by step (1) is sintered 14h at air atmosphere, 1050 DEG C, by crushing after natural cooling,
Obtain the doping cobalt acid lithium substrate that partial size is 13-22 μm；
(3) it presses clad composition and prepares mixed metal oxalate solution, concentration 0.042mol/L；NaOH solution, concentration
For 0.42mol/L；The lithium hydroxide solution of 0.42mol/L is added in reaction kettle, then by the acid of cobalt obtained by (2) the step of 2kg
Lithium substrate is added thereto, and stirs 30min；Mixed metal solution, H2O2It is added in reaction kettle with NaOH solution cocurrent.Reaction process
Middle control pH is 12~13, mixing speed 400r/min, and temperature of reaction kettle is 90 DEG C.Slurry is obtained after reaction 20h filtering, i.e.,
For secondary mixture；
(4) secondary mixture obtained by step (3) is sintered 10h at 980 DEG C, obtains lithium cobalt positive polar material
Material.
Embodiment 5
The lithium cobalt positive polar material of embodiment 5, substrate Li1.001Co0.994Y0.002Mg0.002Al0.002O2, packet
Coating is the LiNi for accounting for substrate mass 0.1%1/3Co1/3Mn1/3O2。
5 lithium cobalt positive polar material of embodiment the preparation method comprises the following steps:
(1) 2000g cobaltosic oxide, 960g lithium carbonate, 5.6g yttrium oxide, 2.9g magnesium hydroxide, 2.5g tri- is weighed to aoxidize
Two aluminium are uniformly mixed, obtain uniform mixture；
(2) mixture obtained by step (1) is sintered 14h at air atmosphere, 1050 DEG C, by crushing after natural cooling,
Obtain the doping cobalt acid lithium substrate that partial size is 13-22 μm；
(3) it presses clad composition and prepares mixed metal oxalate solution, concentration 0.042mol/L；NaOH solution, concentration
For 0.42mol/L；The lithium hydroxide solution of 0.42mol/L is added in reaction kettle, then by the acid of cobalt obtained by (2) the step of 2kg
Lithium substrate is added thereto, and stirs 30min；Mixed metal solution, H2O2It is added in reaction kettle with NaOH solution cocurrent.Reaction process
Middle control pH is 12~13, mixing speed 400r/min, and temperature of reaction kettle is 90 DEG C.Slurry is obtained after reaction 20h filtering, i.e.,
For secondary mixture；
(4) secondary mixture obtained by step (3) is sintered 10h at 1000 DEG C, obtains lithium cobalt positive polar material
Material.
Comparative example 1
The lithium cobalt positive polar material of this comparative example, chemical formula Li1.001Co0.995Mg0.002Al0.003O2。
The lithium cobalt positive polar material of comparative example 1 the preparation method comprises the following steps:
(1) 2000g cobaltosic oxide, 960g lithium carbonate, 2g magnesia, 3.8g aluminum oxide are weighed, is uniformly mixed, obtains
To uniform mixture；
(2) mixture obtained by step (1) is sintered 16h at air atmosphere, 1040 DEG C, by crushing after natural cooling,
Obtain the lithium cobalt positive polar material for the comparative example that partial size is 13-22 μm.
Analysis test
The visible attached drawing 1 of lithium cobalt positive polar material XRD diagram made from embodiment 1, SEM scheme visible attached drawing 2.Comparison
Composite positive pole SEM prepared by example 1 schemes visible attached drawing 3.The magnification ratio of attached drawing 2 and attached drawing 3 is 100000 times.
The positive electrode that embodiment and comparative example is obtained is assembled into button half-cell and comes the discharge capacity of assessment material, head
Effect and cycle performance.The charge-discharge performance test for carrying out battery at room temperature, is filled by the way of first constant current again constant pressure
Electricity, then constant-current discharge is used, voltage range is 3.0V-4.5V；Test process uses 0.1C charge and discharge electro-active two weeks, then with charge and discharge
Electric current density is 0.7C circulation 50 weeks.
Table 1 show the test result of embodiment and comparative example.Attached drawing 4 show embodiment and comparative example lithium cobalt composite oxygen
The cycle performance figure of compound positive electrode.
1 each parameter list of embodiment and comparative example sample of table
Claims (10)
1. a kind of lithium cobalt positive polar material, it is characterised in that: including substrate and account for substrate mass percentage 0.05%
~10% clad；
The chemical formula of substrate is Li1+yCo1-xAxO2；The chemical formula of clad is LiMaM’bM”cO2；
In the chemical formula of substrate, one of A Mg, Al, Ti, Zr, Ni, Mn, Y, V, Mo, W or a variety of；0.001≤x≤0.1,
0≤y≤0.03；
In the chemical formula of clad, M, M ' and M " be respectively selected from any three kinds in Ni, Co, Mn, Al；0 < a < 1,0 <b < 1,0 < c <
1, and a+b+c=1.
2. a kind of lithium cobalt positive polar material according to claim 1, it is characterised in that: the chemical formula of substrate
In, at least two in A Mg, Al, Ti, Y；0.001≤x≤0.1,0≤y≤0.002；In the chemical formula of clad, M is
Ni, M ' it is Co, M " is Mn；1/3≤a≤0.8,0.1≤b≤1/3,0 < c≤1/3, and a+b+c=1.
3. a kind of preparation method of lithium cobalt positive polar material as claimed in claim 1 or 2, it is characterised in that: including with
Lower step:
1) cobalt source, lithium source, doping metals source are uniformly mixed, obtain primary mixture；
2) primary mixture is sintered, obtains doping cobalt acid lithium substrate；
3) lithium source solution, doping cobalt acid lithium substrate, mixed metal solution, oxidant and aqueous slkali are reacted in a kettle, is obtained
To slurry, slurry is dried to obtain secondary mixture；
4) secondary mixture is sintered, obtains lithium cobalt positive polar material.
4. a kind of preparation method of lithium cobalt positive polar material according to claim 3, it is characterised in that: step
1) in, cobalt source is at least one of cobaltosic oxide, cobalt oxide, cobalt carbonate, cobalt acetate；Doping metals source is substrate Li1+ yCo1-xAxO2At least one of the oxide of middle element A, hydroxide, metal salt.
5. a kind of preparation method of lithium cobalt positive polar material according to claim 3, it is characterised in that: step
2) in, sintering is specially that 8h~22h is sintered at 800 DEG C~1060 DEG C in air atmosphere.
6. a kind of preparation method of lithium cobalt positive polar material according to claim 3, it is characterised in that: step
3) in, mixed metal solution is by LiMaM’bM”cO2Metal M, M of composition ', the respective acetate of M ", carbonate, sulfate,
The mixed solution that oxalates, chlorate, chlorate, bicarbonate form；Oxidant is H2O2、NaClO、KClO3、KMnO4In
It is at least one；Alkali is alkali metal hydroxide.
7. a kind of preparation method of lithium cobalt positive polar material according to claim 3 or 6, it is characterised in that:
In step 3), the temperature of reaction is 40 DEG C~150 DEG C, and the time of reaction is 10h~48h, and the pH of reaction is 9~13.
8. a kind of preparation method of lithium cobalt positive polar material according to claim 3, it is characterised in that: step
4) in, sintering is specially that 5h~for 24 hours is sintered at 400 DEG C~1000 DEG C in air atmosphere.
9. a kind of preparation method of lithium cobalt positive polar material according to claim 3, it is characterised in that: step
1) or in step 2), lithium source is at least one of lithium carbonate, lithium nitrate, lithium hydroxide, lithia, lithium oxalate, lithium acetate.
10. a kind of lithium battery, it is characterised in that: lithium cobalt positive polar material just extremely of any of claims 1 or 2.
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