CN105958027B - A kind of manganese base composite positive pole and preparation method thereof - Google Patents
A kind of manganese base composite positive pole and preparation method thereof Download PDFInfo
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- CN105958027B CN105958027B CN201610459045.4A CN201610459045A CN105958027B CN 105958027 B CN105958027 B CN 105958027B CN 201610459045 A CN201610459045 A CN 201610459045A CN 105958027 B CN105958027 B CN 105958027B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- 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
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/48—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to battery material manufacture technology fields, especially a kind of manganese base composite positive pole and preparation method thereof, by manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent, spinel lithium manganate particle proportion, make it possible to form the rich lithium phase of high price as core, in middle layer using spinel lithium manganate particle, forms low price Li in outer layer2MnO2Phase, so that forming internal spinel lithium manganate energy storage, intermediate rich lithium phase energy storage, the outer layer at high price of being formed forms Li2MnO2Phase energy storage, effectively raise the specific capacity of positive electrode, and pass through the material in spinel lithium manganate particle external sheath lower valency, effectively inhibit the decaying of spinel lithium manganate dissolution and the rich lithium phase of middle layer high price, and in phase of the external sheath containing more lithium, so that its rate of decay for effectively improving positive electrode and improving its specific capacity.
Description
Technical field
The present invention relates to battery material manufacture technology field, especially a kind of manganese base composite positive pole and its preparation side
Method.The invention belongs to Electrochemical Engineering and commercial plant field, can be used as electrode active material, is applied to aqueous solution
In the lithium-ion battery system of organic electrolyte or the lithium battery system of organic electrolyte.
Background technique
Since human society marches toward industrialization, the demand to fossil energies such as coal and petroleum is huge, with coal and petroleum etc.
The huge consumption of non-renewable energy resources and resource increasingly lacks.The greenhouse effects of CO2 emission aggravation and increasingly serious sky
The pollution of gas, ecological environment constitutes more severe threat to our the rely earth homes of life.Greatly develop wind
The renewable energy such as energy, solar energy are to realize the important channel of China's energy sustainable development.When renewable energy power generation has
Difference and unstability limit the utilization of its large-scale grid connection.Electric power storage is having for the instability problem of solution renewable energy
One of efficacious prescriptions method is, it can be achieved that renewable energy large-scale application.
With to electric power storage solve renewable sources of energy instability problem research and exploration during, for battery research
Quick development and conceptual phase are stepped into；In the nineties in last century, lithium ion secondary battery obtains industrialization in Japan, because
It receives the favor of people with performances such as high voltage, high capacity, memoryless benefits, especially in portable electronic product, logical
Interrogate Information application etc..
Lithium ion battery makes since its own has the advantages that energy density and energy transformation ratio height, voltage rating are higher
It obtains it and has obtained faster development；And in lithium ion battery, positive electrode is the material of core key, the property of positive electrode
The performance that lithium ion battery can largely be affected, which determine energy force density, service life and safeties of lithium battery etc.
Index, shared cost reaches 30-40% in lithium ion battery.
Mainly there are several bodies such as lithium cobalt oxide, lithium nickel oxygen and lithium manganese oxygen for the research early stage of anode material for lithium-ion batteries
System；Lithium oxygen plus plate material is current quotient since its preparation process is relatively simple, performance is stable, specific capacity is high and cyclicity is good
The positive electrode mainly used in product lithium ion battery, but the price of cobalt is high, safety is poor, especially large-scale, power type electricity
Safety is poor when pond is applied, and is mainly used for miniaturized electronics, it is difficult to promote in the larger application field of the energy storage capacities such as electric vehicle；Lithium
Nickel oxygen (LiNiO2) has layer structure similar with lithium cobalt oxide, and specific energy is high, cycle performance is preferable, moderate, but prepares
The condition of lithium nickel oxygen is extremely harsh, and application is not wide；Lithium manganese-oxygen material have the advantages that abundant raw material, it is low in cost, without environmental hazard,
But it is dissolved at relatively high temperatures causes capacitance loss, and cycle life is not high, and specific capacity is lower, although in the prior art, grinding
The person of studying carefully is doped with elements such as Ni, Co, Cr for this kind of product, improves Li/Mn ratio, achievees the purpose that improve drawbacks described above,
But the specific capacity for still making the lithium manganese-oxygen material of preparation is about 120-130mAh/g, so that the performance of lithium ion battery is poor.
Moreover, the increased costs that the elements such as Ni, Co are doped material are more.
For this purpose, there are other technological means again in the prior art, such as phosphate LiMPO4(M=Fe, Co, Ni, Mn, V
Deng), Li3V2(PO4)3, silicate Li2MSiO4(M=Fe, Mn) and titanate Li2MTiO4(M=Ni, Fe, Mn), but it is above-mentioned existing
There is the specific capacity of the material in technology still lower, and then leads to the specific energy material that is still lower, or even having of the battery of preparation
Material can also be excessively high because of current potential, leads to electrolyte decomposition, so that battery occurs the phenomenon that shortening.
The reason of causing above-mentioned phenomenon to occur, is: the either LiMO of stratiform2(including LiCoO2、LiNi1/3Co1/3Mn1/3O2
Ex hoc genus anne object) or spinel-type LiMn2O4Or the LiMPO of olivine-type4Deng each of which molecule contains only one
The transition element atom of a variable 1 valence, enables the lithium ion removed in charging to be up to one, molecular weight is the smallest
LiMO2, theoretical specific capacity is 274mAh/g or so, so that it, in the stability for ensuring crystal structure, can be removed
Lithium ion is only 0.5-0.65, so that its actual specific capacity is 140mAh/g or so, is caused using it as anode material
Expect that the specific energy of the battery of preparation is lower；Also, the solid-solution material or olivine-type material etc. of stratiform and spinelle, in its tool
There are the trivalent, tetravalence and when appraising at the current rate of M of rich lithium manganese, enable to its specific capacity higher, still, this kind of material is prepared into battery
Afterwards, since the voltage of rich lithium manganese material is higher, it is easy to cause electrolyte decomposition, special capacity fade is very fast, so that the battery of preparation
Service life it is poor.
In consideration of it, this researcher provides specific capacity height, cost by the way that manganese based combined electrode material is studied and explored
It is low, active it is high, can effectively avoid electrolyte decomposition, reduce the manganese base composite positive pole of special capacity fade speed, be lithium from
Sub- positive electrode for battery material, which is received, provides a kind of new approaches.
Summary of the invention
In order to solve the above technical problems existing in the prior art, the present invention provide a kind of manganese base composite positive pole and
Preparation method.
It is emerged from particular by following technical scheme:
A kind of manganese base composite positive pole is manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent composition covering packet
Overlay on outside spinel lithium manganate particle, wherein manganese source, lithium source, chromium source, the proportion in lanthanum source be so that lithium in covering, lanthanum, chromium and
The atomic ratio of manganese is 1.91-1.55: 0.03-0.15: 0.03-0.15: 0.97-0.85；Wherein the dosage of adhesive is manganese source, lithium
Source, chromium source, the mass percent of the total dosage in lanthanum source are calculated as 1-10%, and the dosage of solvent is that manganese source, lithium source, chromium source, lanthanum source are always used
The quality of amount is calculated as 5-50 times.So that the outer layer manganese in the manganese base composite positive pole obtained is in compared with lower valency, and contain
Multiple available lithium ions, improve the specific capacity of positive electrode.By chromium source, the processing of lanthanum source doping, so that being formed internal
Spinel lithium manganate energy storage, intermediate rich lithium phase energy storage, the outer layer at high price of being formed form Li2MnO2Phase energy storage, effectively raises anode
The specific capacity of material, and by the material in spinel lithium manganate particle external sheath lower valency, effectively inhibit spinelle
LiMn2O4 dissolution and the decaying of the rich lithium phase of middle layer high price, and in phase of the external sheath containing more lithium, so that it is effectively improved
The rate of decay of positive electrode and improve its specific capacity.
Above-mentioned use is coated on outside spinel lithium manganate, is to reach by being coated on outside spinel lithium manganate particle
To the stress for mitigating volume change, the high price richness lithium phase of middle layer, the Li of outer layer are prevented2MnO2The mutually volume change in charge and discharge
Greatly, fast charging and discharging is easy to cause breakage of particles, so that the defect of specific capacity rapid decay, reduces height ratio capacity material and pair occurs
The probability of reaction and decaying.
The preparation method of above-mentioned manganese base composite positive pole is to put into adhesive in solvent, is dissolved into solution, then to
Spinel lithium manganate particle is wherein added, stirs into suspension, and manganese source, lithium source, chromium source, lanthanum source is added, during the addition process,
Temperature is controlled at 0-120 DEG C, after the completion of to be added, adjustment temperature is 60-200 DEG C, and solvent is steamed completely, is passed through protectiveness gas
Body is warming up to 600-1200 DEG C, isothermal reaction 0.5-48h, and cooling is ground into 6-15 microns, obtains manganese base composite positive pole.
Raw material is bonded in internal layer spinel lithium manganate particle surface by adhesive, is especially first dissolved into adhesive using solvent
After solution, spinel lithium manganate particle is added, suspension is stirred into, adds manganese source, lithium source, chromium source, lanthanum source, then adjust temperature
Degree is handled, and not only so as to uniformly coat, additionally provides reducing agent, so that with the variation of temperature, it is therein viscous
Mixture is decomposed, and reducibility gas and carbon is decomposited, and by the manganese of high temperature reduction high-valence state, chromium, so that in positive electrode
Outer layer formed lower valency doping Li2MnO2Phase, while the carbon that adhesive itself decomposes, will be uniformly coated on outer layer,
Improve the electron conduction of composite positive pole；Meanwhile adhesive, in decomposable process, portion gas is escaped, in positive electrode
Surface form tiny hole, increase the specific surface area of positive electrode, enable active material and electricity inside positive electrode
Adequately contact occurs for electrolyte solution.
In above-mentioned temperature-rise period, heating rate is 0.1-200 DEG C/min.
Above-mentioned heating rate uses electric heating to heat up in 0.1-20 DEG C/min, is 20 DEG C/min in heating rate
When above, microwave heating heating treatment is used.
It is handled by using above-mentioned heating mode, so that the primary of manganese base composite positive pole during the high temperature treatment process
Granular size is easily controllable, and avoiding high-temperature process causes spinel lithium manganate particle kernel complete by reaction conversion, additionally it is possible to
Promote quickly to generate middle layer and outer layer, so that tap density height, middle layer and the outer layer of the positive electrode obtained were formed
Secondary granule is uniform in size, and the loading density of positive electrode is higher.
Above-mentioned manganese source is manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, hydroxyl manganese oxide, nitric acid
At least one of manganese, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate, high manganese lithium, LiMn2O4, spinel lithium manganate.
Above-mentioned lithium source is at least one of lithium nitrate, lithium oxalate, lithium carbonate, lithium formate, lithium acetate, lithium hydroxide.
Above-mentioned chromium source is at least one of chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate, chromic formate, chromium acetate.
Above-mentioned lanthanum source is at least one of lanthana, lanthanum nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum, lanthanum acetate.
Above-mentioned adhesive is polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, furfural resin, polyacrylic acid
At least one of resin, polyurethane resin, polyvinyl alcohol.
Above-mentioned solvent is water, ethyl alcohol, propyl alcohol, ethylene glycol, glycerine, benzene, toluene, acetone, methyl ethyl ketone, butanone, chloromethane
Alkane, benzoyl, formic acid, n,N-Dimethylformamide, at least one of N-Methyl pyrrolidone.
Above-mentioned spinel lithium manganate granular size is 0.3-10 microns.
The size of the manganese base composite positive pole particle of above-mentioned acquisition is 6-15 microns.
Above-mentioned protective gas is at least one of air, oxygen, nitrogen, argon gas, helium, carbon dioxide, hydrogen；
Selection by the protective gas be passed through so that the valence state of the oxide of manganese is at Utopian valence state, avoid
The oxide of manganese base composite positive pole outer layer manganese exists at 520 DEG C or more with the mixed valence of trivalent or trivalent and tetravalence, really
The outer layer protected in positive electrode forms Li2MnO2Phase, improves the performance of positive electrode, while ensuring to form high price in middle layer rich
Lithium phase.
In order to make the structure of manganese base composite positive pole more stable, the positive electrode is improved as lithium battery
The performance of the battery of positive electrode preparation, such as specific capacity, service life；It is dissolved by adhesive during the preparation process
After solution, before spinel lithium manganate particle is added, further include the steps that aluminium salt, zinc salt and/or magnesium salts is added.Wherein plus
Enter the 0-5% that amount accounts for lithium source quality respectively.The amount of above-mentioned addition aluminium salt, zinc salt and/or magnesium salts cannot be excessive, otherwise will shadow
Ring the specific capacity of composite positive pole.
It is above-mentioned to be warming up to when being handled at 600-1200 DEG C, it can be placed in closed container under protective gas existence condition
Carry out heat-agglomerating reaction；Saggar can also be put into and be placed in the equipment such as the kiln of gas shield, wherein protective gas exists
Line flow velocity in reaction chamber is not less than 5cm/min.
The input amount of above-mentioned spinel lithium manganate particle, accounts for 0.01-0.019 times of solvent by quality ratio.
Compared with prior art, technical effect of the invention is embodied in:
By manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent, spinel lithium manganate particle proportion, make it possible to
Spinel lithium manganate particle is core, in the rich lithium phase of middle layer formation high price, forms low price Li in outer layer2MnO2Phase, so that in being formed
Portion's spinel lithium manganate energy storage, intermediate rich lithium phase energy storage, the outer layer at high price of being formed form Li2MnO2Phase energy storage, effectively raises just
The specific capacity of pole material, and by the material in spinel lithium manganate particle external sheath lower valency, effectively inhibit sharp crystalline substance
The dissolution of stone LiMn2O4 and the decaying of the rich lithium phase of middle layer high price, and in phase of the external sheath containing more lithium, so that it is effectively
It improves the rate of decay of positive electrode and improves its specific capacity.
The preparation method of the manganese base composite positive pole of the invention is easy to operate, process is short, and low energy consumption, and makes
The manganese of manganese base composite positive pole outer layer is in compared with lower valency, and contains more than one available lithium ion, effective to improve
The specific capacity of positive electrode, and using spinel lithium manganate as core, in conjunction with parameters such as treatment temperatures in preparation process
Define, avoiding high-temperature process causes spinel lithium manganate particle kernel complete by reaction conversion, additionally it is possible to promote quick
Middle layer and outer layer are generated, so that the secondary granule that tap density height, middle layer and the outer layer of the positive electrode obtained are formed is big
Small uniform, the loading density of positive electrode is higher；The stress for mitigating volume change, prevents high price richness lithium phase, the outer layer of middle layer
Li2MnO2Mutually volume change is big in charge and discharge, and fast charging and discharging is easy to cause breakage of particles, so that specific capacity rapid decay
Defect, reduce height ratio capacity material occur side reaction and decaying probability.In addition, because of the manganese base anode composite of the invention
Material outer layer contains more than one available lithium ion, it is possible to provide additional more lithium, the high ratio that can be used first charge discharge efficiency low
The battery system of capacity negative electrode material composition high-energy-density.
The preparation process of the invention is simple, at low cost, pollution is few, can be applied to organic electrolyte or water
In the battery system of solution, activity is higher, and specific capacity is higher.
Specific embodiment
It is limited below with reference to specific embodiment technical solution of the present invention is further, but claimed
Range is not only limited to made description.
Embodiment 1
At room temperature, use 500g concentration that 1.7g phenolic resin is dissolved into solution for 95% ethyl alcohol；It is again that 5g particle is big
The small spinel lithium manganate for concentrating on 0.3-10 microns is added, and stirring forms suspension, then by manganese acetate, lithium hydroxide, nitric acid
Chromium, lanthanum nitrate are added, and the atomic ratio for controlling lithium, lanthanum, chromium and manganese is 1.91: 0.03: 0.03: 0.97, and adding manner is by acetic acid
After manganese, chromic nitrate, lanthanum nitrate are pre-mixed uniformly, stirring 30min is added, after lithium hydroxide is dissolved with 350g water, is added,
Constant temperature stirs into suspension；
Above-mentioned suspension is heated to 80 DEG C of processing, so that phenolic resin, which uniformly bonds deposit, is coated on spinelle
Lithium manganate particle surface, processing time are until solvent evaporation completely, obtains presoma；
Above-mentioned presoma is placed in microwave kiln, is heated by protective gas of nitrogen, nitrogen is in microwave kiln
Line flow velocity in furnace is 5cm/min, and uses microwave heating treatment, and heating rate is 50 DEG C/min, is heated to 1200 DEG C, constant temperature
0.5h is reacted, and after being cooled to room temperature under nitrogen protection, is ground into 6-15 micron, acquisition manganese base composite positive pole.
Above-mentioned manganese base composite positive pole is mixed with conductive agent carbon black, adhesive PVDF, ratio is manganese base anode composite
Material: carbon black: PTFE=80: 15: 7, it is sized mixing and is coated on 20 microns of thick aluminium foils with N-Methyl pyrrolidone grinding, preparation
At test electrode.Above-mentioned electrode is cut into the circle sheet of diameter 14mm, with 0.5MPa pressure compacting after can be used as lithium from
Sub- anode is tested.Using the electrode as positive, lithium piece as cathode, PC/DME/LiPF6It is made as electrolyte
2032 type button cells, the constant current 10mA/g charge-discharge test between 2.5-4.2V, specific discharge capacity are greater than 200mAh/g.
Embodiment 2
At room temperature, use 300g concentration that 0.85g phenolic resin is dissolved into solution for 95% ethyl alcohol；It is again that 5g particle is big
The small spinel lithium manganate for concentrating on 0.3-10 microns is added, and stirring forms suspension, then by manganese acetate, lithium hydroxide, nitric acid
Chromium, lanthanum nitrate are added, and the atomic ratio for controlling lithium, lanthanum, chromium and manganese is 1.91: 0.03: 0.03: 0.97, and adding manner is by acetic acid
After manganese, chromic nitrate, lanthanum nitrate are pre-mixed uniformly, stirring 30min is added, after lithium hydroxide is dissolved with 125g water, is added,
Constant temperature stirs into suspension；
Above-mentioned suspension is heated to 60 DEG C of processing, so that phenolic resin, which uniformly bonds deposit, is coated on spinelle
Lithium manganate particle surface, processing time are until solvent evaporation completely, obtains presoma；
Above-mentioned presoma is placed in muffle furnace, is heated by protective gas of nitrogen, nitrogen is in muffle furnace
Line flow velocity be 5cm/min, and heating treatment, heating rate is 0.1 DEG C/min, be heated to 600 DEG C, isothermal reaction 48h, and
After being cooled to room temperature under nitrogen protection, 6-15 microns are ground into, obtains manganese base composite positive pole.
Above-mentioned manganese base composite positive pole is mixed with conductive agent carbon black, adhesive PVDF, ratio is manganese base anode composite
Material: carbon black: PTFE=80: 15: 7, it is sized mixing and is coated on 20 microns of thick aluminium foils with N-Methyl pyrrolidone grinding, preparation
At test electrode.Above-mentioned electrode is cut into the circle sheet of diameter 14mm, with 0.5MPa pressure compacting after can be used as lithium from
Sub- anode is tested.Using the electrode as positive, lithium piece as cathode, PC/DME/LiPF6It is made as electrolyte
2032 type button cells, the constant current 10mA/g charge-discharge test between 2.5-4.2V, specific discharge capacity are greater than 200mAh/g.
Embodiment 3
At room temperature, use 500g concentration that 0.85g phenolic resin is dissolved into solution for 95% ethyl alcohol；It is again that 5g particle is big
The small spinel lithium manganate for concentrating on 0.3-10 microns is added, and stirring forms suspension, then by manganese acetate, lithium hydroxide, nitric acid
Chromium, lanthanum nitrate are added, and the atomic ratio for controlling lithium, lanthanum, chromium and manganese is 1.55: 0.15: 0.15: 0.85, and adding manner is by acetic acid
After manganese, chromic nitrate, lanthanum nitrate are pre-mixed uniformly, stirring 30min is added, after lithium hydroxide is dissolved with 250g water, is added,
Constant temperature stirs into suspension；
Above-mentioned suspension is heated to 80 DEG C of processing, so that phenolic resin, which uniformly bonds deposit, is coated on spinelle
Lithium manganate particle surface, processing time are until solvent evaporation completely, obtains presoma；
Above-mentioned presoma is placed in micro-wave oven, is heated by protective gas of nitrogen, nitrogen is in micro-wave oven
Line flow velocity be not less than 5cm/min, and use microwave heating treatment, heating rate be 60 DEG C/min, be heated to 850 DEG C, constant temperature
0.5h is reacted, and after being cooled to room temperature under nitrogen protection, is ground into 6-15 micron, acquisition manganese base composite positive pole.
Above-mentioned manganese base composite positive pole is mixed with conductive agent carbon black, adhesive PVDF, ratio is manganese base anode composite
Material: carbon black: PTFE=80: 15: 7, it is sized mixing and is coated on 20 microns of thick aluminium foils with N-Methyl pyrrolidone grinding, preparation
At test electrode.Above-mentioned electrode is cut into the circle sheet of diameter 14mm, with 0.5MPa pressure compacting after can be used as lithium from
Sub- anode is tested.Using the electrode as positive, lithium piece as cathode, PC/DME/LiPF6It is made as electrolyte
2032 type button cells, the constant current 10mA/g charge-discharge test between 2.5-4.2V, specific discharge capacity are greater than 190mAh/g.
Embodiment 4
At room temperature, use 275g concentration that 0.85g phenolic resin is dissolved into solution for 95% ethyl alcohol；It is again that 5g particle is big
The small spinel lithium manganate for concentrating on 0.3-10 microns is added, and stirring forms suspension, then by manganese acetate, lithium hydroxide, nitric acid
Chromium, lanthanum nitrate are added, and the atomic ratio for controlling lithium, lanthanum, chromium and manganese is 1.55: 0.15: 0.15: 0.85, and adding manner is by acetic acid
After manganese, chromic nitrate, lanthanum nitrate are pre-mixed uniformly, stirring 30min is added, after lithium hydroxide is dissolved with 100g water, is added,
Constant temperature stirs into suspension；
Above-mentioned suspension is heated to 80 DEG C of vacuumize processs, is coated on so that phenolic resin uniformly bonds deposit
Spinel lithium manganate particle surface, processing time are until solvent evaporation completely, obtains presoma；
Above-mentioned presoma is placed in micro-wave oven, is heated by protective gas of nitrogen, nitrogen is in micro-wave oven
Line flow velocity be not less than 5cm/min, and use microwave heating treatment, heating rate is 200 DEG C/min, is heated to 1200 DEG C, permanent
Temperature reaction 0.5h, and after being cooled to room temperature under nitrogen protection, 6-15 micron are ground into, acquisition manganese base composite positive pole.
Above-mentioned manganese base composite positive pole is mixed with conductive agent carbon black, adhesive PVDF, ratio is manganese base anode composite
Material: carbon black: PTFE=80: 15: 7, it is sized mixing and is coated on 20 microns of thick aluminium foils with N-Methyl pyrrolidone grinding, preparation
At test electrode.Above-mentioned electrode is cut into the circle sheet of diameter 14mm, with 0.5MPa pressure compacting after can be used as lithium from
Sub- anode is tested.Using the electrode as positive, lithium piece as cathode, PC/DME/LiPF6It is made as electrolyte
2032 type button cells, the constant current 10mA/g charge-discharge test between 2.5-4.2V, specific discharge capacity are greater than 260mAh/g.
Embodiment 5
At room temperature, use 275g concentration that 0.85g phenolic resin is dissolved into solution for 95% ethyl alcohol；It is again that 5g particle is big
The small spinel lithium manganate for concentrating on 0.3-10 microns is added, and stirring forms suspension, then by manganese acetate, lithium hydroxide, nitric acid
Chromium, lanthanum nitrate are added, and the atomic ratio for controlling lithium, lanthanum, chromium and manganese is 1.55: 0.15: 0.15: 0.85, and adding manner is by acetic acid
After manganese, chromic nitrate, lanthanum nitrate are pre-mixed uniformly, stirring 30min is added, after lithium hydroxide is dissolved with 100g water, is added,
Constant temperature stirs into suspension；ANN aluminium nitrate nonahydrate 1.57g is weighed, with being added after 50g deionized water dissolving；
Above-mentioned suspension is heated to 80 DEG C of vacuumize processs, is coated on so that phenolic resin uniformly bonds deposit
Spinel lithium manganate particle surface, processing time are until solvent evaporation completely, obtains presoma；
Above-mentioned presoma is placed in micro-wave oven, is heated by protective gas of nitrogen, nitrogen is in micro-wave oven
Line flow velocity be not less than 5cm/min, and use microwave heating treatment, heating rate is 200 DEG C/min, is heated to 1200 DEG C, permanent
Temperature reaction 0.5h, and after being cooled to room temperature under nitrogen protection, 6-15 micron are ground into, acquisition manganese base composite positive pole.
Above-mentioned manganese base composite positive pole is mixed with conductive agent carbon black, adhesive PVDF, ratio is manganese base anode composite
Material: carbon black: PTFE=80: 15: 7, it is sized mixing and is coated on 20 microns of thick aluminium foils with N-Methyl pyrrolidone grinding, preparation
At test electrode.Above-mentioned electrode is cut into the circle sheet of diameter 14mm, with 0.5MPa pressure compacting after can be used as lithium from
Sub- anode is tested.Using the electrode as positive, lithium piece as cathode, PC/DME/LiPF6It is made as electrolyte
2032 type button cells, the constant current 10mA/g charge-discharge test between 2.5-4.2V, specific discharge capacity are greater than 250mAh/g.
Embodiment 6
A kind of manganese base composite positive pole is manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent composition covering packet
Overlay on outside spinel lithium manganate particle, wherein manganese source, lithium source, chromium source, the proportion in lanthanum source be so that lithium in covering, lanthanum, chromium and
The atomic ratio of manganese is 1.73: 0.07: 0.11: 0.91；Wherein the dosage of adhesive is manganese source, lithium source, chromium source, the total dosage in lanthanum source
Mass percent is calculated as 9%, and the dosage of solvent is manganese source, lithium source, chromium source, the quality of the total dosage in lanthanum source are calculated as 20 times.
The manganese source is manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, hydroxyl manganese oxide, nitric acid
Manganese, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate any mass mixing.
The lithium source is any mass mixing of lithium nitrate, lithium oxalate, lithium carbonate, lithium formate.
The chromium source is any mass mixing of chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate.
The lanthanum source is any mass mixing of lanthana, lanthanum nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum.
The adhesive is any matter of polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, furfural resin
Amount mixing.
The solvent is any mass mixing of water, ethyl alcohol, propyl alcohol.
Adhesive is put into solvent, is dissolved into solution by preparation method, then spinel lithium manganate particle is added thereto,
Suspension is stirred into, and manganese source, lithium source, chromium source, lanthanum source is added, during the addition process, control temperature is at 80 DEG C, completion to be added
Afterwards, adjustment temperature is 150 DEG C, and solvent is steamed completely, is passed through protective gas and is warming up to 900 DEG C, isothermal reaction 33h, cool down,
6-15 microns are ground into, manganese base composite positive pole is obtained.
In above-mentioned temperature-rise period, heating rate is 100 DEG C/min.The investment of above-mentioned spinel lithium manganate particle
Amount, accounts for 0.015 times of solvent by quality ratio.Above-mentioned spinel lithium manganate granular size is 0.3-10 microns.Above-mentioned guarantor
Shield property gas is helium, carbon dioxide, any mass mixing in hydrogen.
Embodiment 7
A kind of manganese base composite positive pole is manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent composition covering packet
Overlay on outside spinel lithium manganate particle, wherein manganese source, lithium source, chromium source, the proportion in lanthanum source be so that lithium in covering, lanthanum, chromium and
The atomic ratio of manganese is 1.87: 0.08: 0.09: 0.99；Wherein the dosage of adhesive is manganese source, lithium source, chromium source, the total dosage in lanthanum source
Mass percent is calculated as 10%, and the dosage of solvent is manganese source, lithium source, chromium source, the quality of the total dosage in lanthanum source are calculated as 50 times.
The manganese source is manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, hydroxyl manganese oxide, nitric acid
Any mass mixing of manganese, manganese oxalate.
The lithium source is any mass mixing of lithium nitrate, lithium oxalate.
The chromium source is any mass mixing of chromium oxide, chromic nitrate, chromium+oxalic acid.
The lanthanum source is any mass mixing of lanthana, lanthanum nitrate, lanthanum oxalate, lanthanum carbonate.
The adhesive is polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, furfural resin, polyacrylic acid
At least one of resin, polyurethane resin, polyvinyl alcohol.
The solvent is any mass mixing of water, ethyl alcohol, propyl alcohol, ethylene glycol.
Adhesive is put into solvent, is dissolved into solution by preparation method, then spinel lithium manganate particle is added thereto,
Suspension is stirred into, and manganese source, lithium source, chromium source, lanthanum source is added, during the addition process, control temperature is to be added complete at 120 DEG C
Cheng Hou, adjustment temperature are 200 DEG C, and solvent is steamed completely, protective gas is passed through and is warming up to 1200 DEG C, isothermal reaction 48h, cold
But, 6-15 microns are ground into, manganese base composite positive pole is obtained.
In above-mentioned temperature-rise period, heating rate is 200 DEG C/min.The investment of above-mentioned spinel lithium manganate particle
Amount, accounts for 0.019 times of solvent by quality ratio.Above-mentioned spinel lithium manganate granular size is 0.3-10 microns.Above-mentioned guarantor
Shield property gas is any mass mixing of argon gas, helium, carbon dioxide.
Embodiment 8
A kind of manganese base composite positive pole is manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent composition covering packet
Overlay on outside spinel lithium manganate particle, wherein manganese source, lithium source, chromium source, the proportion in lanthanum source be so that lithium in covering, lanthanum, chromium and
The atomic ratio of manganese is 1.91: 0.03: 0.03: 0.97；Wherein the dosage of adhesive is manganese source, lithium source, chromium source, the total dosage in lanthanum source
Mass percent is calculated as 1%, and the dosage of solvent is manganese source, lithium source, chromium source, the quality of the total dosage in lanthanum source are calculated as 5 times.
The manganese source is manganese monoxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, manganese dioxide, hydroxyl manganese oxide, nitric acid
Manganese, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate, high manganese lithium, LiMn2O4, spinel lithium manganate any mass mixing.
The lithium source is lithium nitrate, any quality of lithium oxalate, lithium carbonate, lithium formate, lithium acetate, lithium hydroxide is mixed
It closes.
The chromium source is any mass mixing of chromium oxide, chromic nitrate, chromium+oxalic acid, chromium carbonate, chromic formate, chromium acetate.
The lanthanum source is any mass mixing of lanthana, lanthanum nitrate, lanthanum oxalate, lanthanum carbonate, formic acid lanthanum, lanthanum acetate.
The adhesive is polyacrylonitrile, phenolic resin, epoxy resin, polyvinyl resin, furfural resin, polyacrylic acid
Resin, polyurethane resin, polyvinyl alcohol any mass mixing.
The solvent is water, ethyl alcohol, propyl alcohol, ethylene glycol, glycerine, benzene, toluene, acetone, methyl ethyl ketone, butanone, chloromethane
Alkane, benzoyl, formic acid, n,N-Dimethylformamide, N-Methyl pyrrolidone any mass mixing.
Adhesive is put into solvent, is dissolved into solution by preparation method, then spinel lithium manganate particle is added thereto,
Suspension is stirred into, and manganese source, lithium source, chromium source, lanthanum source is added, during the addition process, control temperature is at 5 DEG C, completion to be added
Afterwards, adjustment temperature is 60 DEG C, and solvent is steamed completely, is passed through protective gas and is warming up to 600 DEG C, isothermal reaction 0.5h, cool down,
6-15 microns are ground into, manganese base composite positive pole is obtained.
In above-mentioned temperature-rise period, heating rate is 0.1 DEG C/min.The investment of above-mentioned spinel lithium manganate particle
Amount, accounts for 0.01 times of solvent by quality ratio.Above-mentioned spinel lithium manganate granular size is 0.3-10 microns.Above-mentioned protection
Property gas is air, oxygen, nitrogen, argon gas, helium, carbon dioxide, any mass mixing in hydrogen.
Embodiment 9
On the basis of the above embodiments 6, other are with embodiment 6, in order to make manganese base composite positive pole
Structure it is more stable, improve the performance for the battery that the positive electrode is prepared as anode material of lithium battery, such as specific capacity makes
With service life etc.；Its during the preparation process, after adhesive is dissolved into solution, before spinel lithium manganate particle is added,
Further include the steps that magnesium salts is added.Wherein additional amount accounts for the 0.1% of lithium source quality respectively.The amount of above-mentioned addition aluminium salt cannot mistake
It is more, it otherwise will will affect the specific capacity of composite positive pole.
Embodiment 10
On the basis of the above embodiments 6, other are with embodiment 6, in order to make manganese base composite positive pole
Structure it is more stable, improve the performance for the battery that the positive electrode is prepared as anode material of lithium battery, such as specific capacity makes
With service life etc.；Its during the preparation process, after adhesive is dissolved into solution, before spinel lithium manganate particle is added,
Further include the steps that aluminium salt, zinc salt and magnesium salts is added.Wherein additional amount accounts for the 4% of lithium source quality respectively.Above-mentioned addition aluminium salt,
The amount of zinc salt and magnesium salts cannot be excessive, otherwise will will affect the specific capacity of composite positive pole.
Embodiment 11
On the basis of the above embodiments 6, other are with embodiment 6, in order to make manganese base composite positive pole
Structure it is more stable, improve the performance for the battery that the positive electrode is prepared as anode material of lithium battery, such as specific capacity makes
With service life etc.；Its during the preparation process, after adhesive is dissolved into solution, before spinel lithium manganate particle is added,
Further include the steps that aluminium salt, zinc salt is added.Wherein additional amount accounts for the 5% of lithium source quality respectively.In above-mentioned addition aluminium salt, zinc salt
Amount cannot be excessive, otherwise will will affect the specific capacity of composite positive pole.
Claims (8)
1. a kind of manganese base composite positive pole, which is characterized in that it is manganese source, lithium source, chromium source, lanthanum source, adhesive, solvent composition
Covering is coated on outside spinel lithium manganate particle, wherein manganese source, lithium source, chromium source, the proportion in lanthanum source be so that lithium in covering,
The atomic ratio of lanthanum, chromium and manganese is 1.91-1.55: 0.03-0.15: 0.03-0.15: 0.97-0.85；Wherein the dosage of adhesive is
Manganese source, lithium source, chromium source, the mass percent of the total dosage in lanthanum source are calculated as 1-10%, and the dosage of solvent is manganese source, lithium source, chromium source, lanthanum
The quality of the total dosage in source is calculated as 5-50 times；
Adhesive is put into solvent, is dissolved into solution by the preparation method of the manganese base composite positive pole, then is added thereto
Enter spinel lithium manganate particle, stir into suspension, and manganese source, lithium source, chromium source, lanthanum source is added, during the addition process, control temperature
Degree is at 0-120 DEG C, and after the completion of to be added, adjustment temperature is 60-200 DEG C, and solvent is steamed completely, is passed through protective gas heating
To 600-1200 DEG C, isothermal reaction 0.5-48h, cooling is ground into 6-15 microns, obtains manganese base composite positive pole.
2. manganese base composite positive pole as described in claim 1, which is characterized in that the manganese source is manganese monoxide, three oxygen
Change two manganese, mangano-manganic oxide, manganese dioxide, hydroxyl manganese oxide, manganese nitrate, manganese oxalate, manganese carbonate, formic acid manganese, manganese acetate, Gao Meng
At least one of sour lithium, LiMn2O4.
3. manganese base composite positive pole as described in claim 1, which is characterized in that the lithium source be lithium nitrate, lithium oxalate,
At least one of lithium carbonate, lithium formate, lithium acetate, lithium hydroxide.
4. manganese base composite positive pole as described in claim 1, which is characterized in that the chromium source be chromium oxide, chromic nitrate,
At least one of chromium+oxalic acid, chromium carbonate, chromic formate, chromium acetate.
5. manganese base composite positive pole as described in claim 1, which is characterized in that the lanthanum source be lanthana, lanthanum nitrate,
At least one of lanthanum oxalate, lanthanum carbonate, formic acid lanthanum, lanthanum acetate.
6. manganese base composite positive pole as described in claim 1, which is characterized in that the adhesive is polyacrylonitrile, phenol
Urea formaldehyde, epoxy resin, polyvinyl resin, furfural resin, polyacrylic resin, polyurethane resin, polyvinyl alcohol at least one
Kind.
7. manganese base composite positive pole as described in claim 1, which is characterized in that the solvent be water, ethyl alcohol, propyl alcohol,
Ethylene glycol, glycerine, benzene, toluene, acetone, methyl ethyl ketone, butanone, chloromethanes, benzoyl, formic acid, n,N-Dimethylformamide, N- first
At least one of base pyrrolidones.
8. manganese base composite positive pole as described in claim 1, which is characterized in that the covering, raw material further include
Aluminium salt, zinc salt or magnesium salts, wherein additional amount accounts for the 0-5% of lithium source quality respectively；After adhesive is dissolved into solution, adding
Before entering spinel lithium manganate particle, further include the steps that aluminium salt, zinc salt or magnesium salts is added.
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| CN113104895A (en) * | 2020-01-13 | 2021-07-13 | 广州汽车集团股份有限公司 | Preparation method of manganous oxide/carbon composite material, negative electrode and lithium ion battery |
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| CN101510606A (en) * | 2009-03-27 | 2009-08-19 | 北京化工大学 | Composite metal oxide coating spinelle type LiMn2O4 anode material and preparation method |
| CN105206821A (en) * | 2015-07-29 | 2015-12-30 | 上海电气集团股份有限公司 | Method for synthesizing lithium ion battery positive electrode material |
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| CN101510606A (en) * | 2009-03-27 | 2009-08-19 | 北京化工大学 | Composite metal oxide coating spinelle type LiMn2O4 anode material and preparation method |
| CN105206821A (en) * | 2015-07-29 | 2015-12-30 | 上海电气集团股份有限公司 | Method for synthesizing lithium ion battery positive electrode material |
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