CN108878852A - A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof - Google Patents
A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof Download PDFInfo
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—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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- 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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Abstract
Present invention relates particularly to a kind of lithium ion battery mangaic acid lithium anode materials and preparation method thereof.The present invention is modified lithium manganate having spinel structure using lower valency element doping, using modified LiMn2O4 as nucleome, while restrained effectively Mn in material outside nucleome with fast-ionic conductor and electronic conductor stacking cladding3+In the Jahn-Teller distortion effect of ion, oxygen defect and electrolyte the problems such as the dissolution of Mn, considerably improve the structural stability of material, and promotion while having taken into account material lithium ion diffusivity and electronic conductivity, two-phase shell and lower valency doping collaboration optimization are modified, and the long circulation life of material can be significantly increased using the syneryistic effect that the two generates.Embodiment the result shows that, capacity retention ratio is up to 98.8% after lithium ion battery nucleocapsid positive electrode provided by the invention recycles 200 times under the conditions of 55 DEG C.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of lithium ion battery mangaic acid lithium anode
Material and preparation method thereof.
Background technique
Electrochmical power source is formd as realizing that it is more mature that energy system of the chemical energy with electric energy conversion and storage has developed
A plurality of heavy-duty battery products, such as widely applied lead-acid battery and nickel-cadmium cell product system.Although these traditional changes
Learning power supply has quality stabilization, high reliability, but can generate during battery product manufacture more serious
Environmental pollution, especially waste battery are dealt with improperly to destruction caused by environment for human survival, and the mankind can be seriously threatened
Life and health.In contrast, lithium ion battery not only has traditional chemical power supply as a kind of novel electrochmical power source system
Good characteristic, while it can be largely avoided the environment of the product systems such as traditional lead acid batteries and nickel-cadmium cell initiation again
The serious problems such as pollution, by concern more and more extensive both at home and abroad.
The performance of positive electrode is most important to the raising of performance of lithium ion battery in lithium ion battery.Spinel-type mangaic acid
Lithium (LiMn2O4) positive electrode is more mature one of anode material for lithium-ion batteries at present, there is such as promoter manganese to enrich,
Technology of preparing is mature, production cost is low, has a safety feature and the advantages that no pollution to the environment.Especially in recent years, country is big
Power develops the strategic new industry such as new energy and new-energy automobile, this is the scale business of lithium manganate having spinel structure positive electrode
Using providing good opportunity.If the material is widely used as anode material for lithium-ion batteries, new one will be made greater efforts to promote
For the research and development of high-performance, low cost and environment-friendly type power lithium-ion battery, and then promote New-energy electric vehicle industry
Fast development.However, the positive electrode high temperature circulation stability is poor, especially high temperature cyclic performance is difficult to meet power lithium battery
The requirement of the long continuation of the journey in pond, seriously constrains the extensive industrial application of the material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of lithium ion battery mangaic acid lithium anode material and its preparation sides
Method, manganate cathode material for lithium provided by the invention have excellent high temperature circulation stability, meet the dynamic lithium battery long continuation of the journey longevity
Life requires.
To achieve the goals above, the present invention provides the following technical solutions：
The present invention provides a kind of lithium ion battery mangaic acid lithium anode materials, including chemical composition is LiMn2-xMxO4Core
Body and two-phase shell；0 x≤0.1 <；The M be lithium ion, positive bivalent metal ion or positive trivalent metal ion, described positive two
Valence metal ion includes magnesium ion, zinc ion or copper ion, and positive trivalent metal ion includes aluminium ion, cobalt ions or chromium ion；
The two-phase shell is the fast-ionic conductor clad and electronic conductor clad of stacking cladding, and the fast ion is led
Body clad is coated on the core surface.
Preferably, fast-ionic conductor includes Li in the two-phase shell2SiO3、La0.7Sr0.3Mn0.7Co0.3O3、
Li1.4Al0.4Ti1.6(PO4)3、Li3PO4Or LaMnO3, electronic conductor includes polypyrrole or polyaniline；
The mass ratio of fast-ionic conductor and electronic conductor is (0.5~2) in the two-phase shell：1.
Preferably, the quality of the two-phase shell is the 1~5% of nucleome quality.
The present invention also provides a kind of preparation methods of lithium ion battery mangaic acid lithium anode material, include the following steps：
(1) mixed powder including lithium source, manganese source and doped source is provided；
The molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,0.1]；
(2) mixed powder that the step (1) obtains successively is pre-sintered and is re-sintered, obtain LiMn2-xMxO4Core
Body；The temperature of the pre-sintering is 400~450 DEG C, and the time of pre-sintering is 4~6h；The temperature re-sintered be 750~
825 DEG C, the time re-sintered is 12~18h；
(3) LiMn obtained in the step (2)2-xMxO4Core surface fabricated in situ fast-ionic conductor clad, obtains
Primary core-shell material；
(4) electronic conductor clad is synthesized in the primary core-shell material surface in situ that the step (3) obtains, obtains mangaic acid
Lithium anode material；
Doped source includes lithium salts, magnesium salts, zinc salt, mantoquita, aluminium salt, cobalt salt, chromic salts or respective metal in the step (1)
Oxide.
Preferably, the temperature being pre-sintered in the step (2) and the temperature re-sintered are reached in a manner of heating up, the liter
The rate of temperature independently is 3~6 DEG C/min.
Preferably, when the electronic conductor clad of fabricated in situ in the step (4) is polypyrrole clad, the original
Position synthesis mode include：
It is molten that the primary core-shell material that the step (3) obtains is added to the ethyl alcohol containing pyrrole monomer and toluenesulfonic acid sodium salt
In liquid, suspension is obtained；
The suspension and ferric salt solution are mixed, oxidative polymerization is carried out.
Preferably, when the electronic conductor clad of fabricated in situ in the step (4) is polyaniline-coated layer, the original
Position synthesis mode include：
Aniline is added after the primary core-shell material that the step (3) obtains is dispersed in water, obtains dispersion feed liquid；
The pH value for adjusting the dispersion feed liquid using hydrochloric acid obtains acid solution to 3~5；
The acid solution is mixed with ammonium persulfate, under the conditions of ice-water bath, carries out cladding precipitating.
Preferably, lithium source includes one of lithium carbonate, lithium hydroxide and lithium acetate or a variety of in the step (1)；
The manganese source include manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, hydroxyl manganese oxide, manganese acetate, manganese carbonate,
One of manganese nitrate and manganese oxalate are a variety of.
Preferably, in the step (1) doped source be respective metal nitrate, acetate or oxide.
Preferably, the preparation method of mixed powder includes in the step (1)：By lithium source, manganese source and doped source anhydrous
It is dry after progress 3~8h of wet ball grinding in ethyl alcohol, obtain drying composite；The drying composite is subjected to dry grinding, is obtained
To mixed powder.
The present invention provides a kind of lithium ion battery mangaic acid lithium anode materials, including chemical composition is LiMn2-xMxO4Core
Body and two-phase shell；0 x≤0.1 <；Wherein M is lithium ion, positive bivalent metal ion or positive trivalent metal ion, and positive divalent
Metal ion includes magnesium ion, zinc ion or copper ion, and positive trivalent metal ion includes aluminium ion, cobalt ions or chromium ion；Institute
State the clad of fast-ionic conductor clad and electronic conductor that two-phase shell is stacking cladding, the fast-ionic conductor clad
It is coated on the core surface.
The present invention is modified lithium manganate having spinel structure using lower valency element doping, using modified LiMn2O4 as core
Body, while Mn in material restrained effectively with fast-ionic conductor and electronic conductor stacking cladding outside nucleome3+Ion
In Jahn-Teller distortion effect, oxygen defect and electrolyte the problems such as the dissolution of Mn, the structure for considerably improving material is steady
It is qualitative, and promotion while taken into account material lithium ion diffusivity and electronic conductivity, two-phase shell and lower valency doping collaboration
Optimization is modified, and the long circulation life of material can be significantly increased using the syneryistic effect that the two generates.Embodiment result table
Bright, capacity retention ratio is up to after lithium ion battery nucleocapsid positive electrode provided by the invention recycles 200 times under the conditions of 55 DEG C
98.8%.
Detailed description of the invention
Fig. 1 is PPy/La prepared by embodiment 10.7Sr0.3Mn0.7Co0.3O3@LiMn1.95Mg0.05O4Process flow chart；
Fig. 2 is PPy/La prepared by embodiment 10.7Sr0.3Mn0.7Co0.3O3@LiMn1.95Mg0.05O4High temperature in 0.5C
Cycle performance figure.
Specific embodiment
The present invention provides a kind of lithium ion battery mangaic acid lithium anode materials, including chemical composition is LiMn2-xMxO4Core
Body and two-phase shell；0 x≤0.1 <；The M be lithium ion, positive bivalent metal ion or positive trivalent metal ion, described positive two
Valence metal ion includes magnesium ion, zinc ion or copper ion, and positive trivalent metal ion includes aluminium ion, cobalt ions or chromium ion；
The two-phase shell is the fast-ionic conductor clad of stacking cladding and the clad of electronic conductor, the fast ion
Conductor is coated on the core surface.
In the present invention, the LiMn2-xMxO4Nucleome in 0 x≤0.1 <, the x is more preferably 0.02~
0.05.In the present invention, the M is positive monovalent metallic ion, positive bivalent metal ion or positive trivalent metal ion；As the M
Be positive monovalent metallic ion when, the positive monovalent metallic ion be lithium ion；It is described when the M is positive bivalent metal ion
Positive bivalent metal ion includes magnesium ion, zinc ion or copper ion；When the M is positive trivalent metal ion, the positive trivalent
Metal ion includes aluminium ion, cobalt ions or chromium ion.
Lithium ion battery mangaic acid lithium anode material provided by the invention includes two-phase shell；The two-phase shell is stacking packet
The fast-ionic conductor clad of core surface and the clad of electronic conductor are overlayed on, the fast-ionic conductor clad is coated on institute
State core surface；In the present invention, electronic conductor is preferably comprised in the fast-ionic conductor clad, is located at fast-ionic conductor packet
Electronic conductor in coating effectively fills up the vacancy of fast-ionic conductor clad, realizes the complete cladding to nucleome；It is described double
Electronic conductor first fills up the vacancy of fast-ionic conductor layer in phase shell, while forming electronics in fast-ionic conductor cover surface and leading
Body clad.In the present invention, fast-ionic conductor preferably includes Li in the two-phase shell2SiO3、
La0.7Sr0.3Mn0.7Co0.3O3、Li1.4Al0.4Ti1.6(PO4)3、Li3PO4Or LaMnO3, the electronic conductor preferably includes polypyrrole
Or polyaniline.In the present invention, the mass ratio of fast-ionic conductor and electronic conductor is preferably (0.5~2) in the two-phase shell:
1, further preferably (0.8~1.3)：1.In the present invention, the quality of the two-phase shell be preferably nucleome quality 1~
5%, further preferably 1.5~4%.
The present invention also provides a kind of preparation methods of lithium ion battery mangaic acid lithium anode material, include the following steps：
(1) mixed powder including lithium source, manganese source and doped source is provided；
The molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,0.1]；
(2) mixed powder that the step (2) obtains successively is pre-sintered and is re-sintered, obtain LiMn2-xMxO4Core
Body；The temperature of the pre-sintering is 400~450 DEG C, and the time of pre-sintering is 4~6h；The temperature re-sintered be 750~
825 DEG C, the time re-sintered is 12~18h；
(3) LiMn obtained in the step (2)2-xMxO4Core surface fabricated in situ fast-ionic conductor clad, obtains
Primary core-shell material；
(4) electronic conductor clad is synthesized in the primary core-shell material surface in situ that the step (3) obtains, obtains mangaic acid
Lithium anode material；
Doped source includes lithium salts, magnesium salts, zinc salt, mantoquita, aluminium salt, cobalt salt, chromic salts or respective metal in the step (1)
Oxide.
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
The present invention provides the mixed powder including lithium source, manganese source and doped source.In the present invention, the lithium source preferably includes
One of lithium carbonate, lithium hydroxide and lithium acetate are a variety of；The manganese source preferably includes manganese dioxide, manganese sesquioxide managnic oxide, four
One of Mn 3 O, hydroxyl manganese oxide, manganese acetate, manganese carbonate, manganese nitrate and manganese oxalate are a variety of.In the present invention, institute
Stating doped source includes lithium salts, magnesium salts, zinc salt, mantoquita, aluminium salt, cobalt salt or chromic salts；The further preferably corresponding gold of the doped source
Nitrate, acetate or the oxide of category.
In the present invention, the molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,
0.1], further preferably 1：1.95~1.98：0.02~0.05；The dosage of the lithium source, manganese source and doped source is respectively to contain
The meter of some elemental lithiums, manganese element and doped metallic elements.
In the present invention, the preparation method of the mixed powder preferably includes：By lithium source, manganese source and doped source in anhydrous second
It is dry after progress 3~8h of wet ball grinding in alcohol, obtain drying composite；The drying composite is subjected to dry grinding, is obtained
Mixed powder.
Lithium source, manganese source and doped source are preferably carried out drying after 3~8h of wet ball grinding by the present invention in dehydrated alcohol, are obtained
Drying composite.In the present invention, the component of the lithium source, manganese source and doped source and dosage are consistent with preceding solution,
This is repeated no more.In the present invention, the dosage of the dehydrated alcohol is to be able to achieve dividing for lithium source, silicon source and doped source mixture
It dissipates, so that wet ball grinding is normally carried out.In the present invention, the time of the wet ball grinding is preferably 3~8h, further excellent
It is selected as 5~6h；The wet ball grinding is sufficiently mixed lithium source, manganese source and doped source.Tool of the present invention to the wet ball grinding
Body embodiment does not have particular/special requirement, using well-known to those skilled in the art.
After wet ball grinding, preferably wet ball grinding feed liquid is dried by the present invention, obtains drying composite.The present invention is to institute
Stating dry specific embodiment does not have particular/special requirement, using the drying mode of ball milling feed liquid well-known to those skilled in the art
?.
After obtaining drying composite, the drying composite is preferably carried out dry grinding by the present invention, obtains mixed powder.
The present invention does not have particular/special requirement to the specific embodiment of the dry grinding, using grinding well-known to those skilled in the art
Mode.
After obtaining mixed powder, the mixed powder is successively pre-sintered and is re-sintered by the present invention, obtains LiMn2- xMxO4Nucleome.In the present invention, the temperature of the pre-sintering is 400~450 DEG C, preferably 420~425 DEG C；The pre-sintering
Time be 4~6h, preferably 4.5~5h.In the present invention, the temperature of the pre-sintering is preferably reached in a manner of heating,
The rate of the heating is preferably 3~6 DEG C/min, further preferably 4~5.5 DEG C/min.
In the present invention, the temperature re-sintered be 750~825 DEG C, preferably 770~820 DEG C, further preferably
780~800 DEG C；The time re-sintered is 12~18h, preferably 13~16h, further preferably 14~15h.In this hair
In bright, the temperature re-sintered preferably is heated up to obtain by the temperature being pre-sintered；The rate of the heating is preferably 3~6 DEG C/
Min, further preferably 4~5 DEG C/min.The present invention can be tied using the step sintering mode re-sintered after being pre-sintered
The LiMn that brilliant degree is good, partial size is more uniform2-xMxO4Nucleome；The M is lithium ion, positive bivalent metal ion or positive trivalent metal
Ion, the positive bivalent metal ion include magnesium ion, zinc ion or copper ion, and positive trivalent metal ion includes aluminium ion, cobalt
Ion or chromium ion.
Obtain LiMn2-xMxO4After nucleome, the present invention is in the LiMn2-xMxO4Core surface fabricated in situ fast-ionic conductor
Clad obtains primary core-shell material.
In the present invention, the fast-ionic conductor clad includes Li in chemical composition2SiO3、
La0.7Sr0.3Mn0.7Co0.3O3、Li1.4Al0.4Ti1.6(PO4)3、Li3PO4Or LaMnO3.When the fast-ionic conductor clad is being changed
Learning is Li on composition2SiO3When, the in-situ synthetic method of the fast-ionic conductor clad preferably includes：
(I) by the LiMn2-xMxO4Nucleome is mixed with dehydrated alcohol, deionized water, obtains nucleome dispersion liquid；
(II) it after mixing the step (I) obtained nucleome dispersion liquid and the alcoholic solution of silicon source, is added dropwise into mixed liquor
Ammonium hydroxide obtains sediment；
(III) sediment that the step (II) obtains is mixed with lithium source, carries out high temperature sintering, in core surface original position
Synthesize fast-ionic conductor clad；The temperature of the high temperature sintering is 700~900 DEG C, and the time of high temperature sintering is 3~10h.
The present invention is preferably by the LiMn2-xMxO4Nucleome is mixed with dehydrated alcohol, deionized water, obtains nucleome dispersion liquid.
The present invention does not have particular/special requirement to the dosage of the dehydrated alcohol, deionized water, to be able to achieve to LiMn2-xMxO4Nucleome it is abundant
Mixing.The present invention does not have particular/special requirement to the hybrid mode, using mode well-known to those skilled in the art.
After obtaining nucleome dispersion liquid, after the present invention preferably mixes the nucleome dispersion liquid and the alcoholic solution of silicon source, to mixed
It closes in liquid and ammonium hydroxide is added dropwise, obtain sediment.In the present invention, the dosage of the silicon source is converted into the content of silicon in silicon source
Li2SiO3Meter is LiMn2-xMxO4The 0.5%~2.8% of nucleome quality, further preferably 1.0%~2.5%.In the present invention
In, solvent is preferably dehydrated alcohol in the alcoholic solution of the silicon source.
The present invention does not have particular/special requirement to the hybrid mode of the alcoholic solution of the nucleome dispersion liquid and silicon source, using this field
The hybrid mode of solution known to technical staff.After the mixing, ammonium hydroxide is added dropwise into mixed liquor by the present invention, is sunk
Starch.
It completes after being added dropwise, solid product is preferably washed and dried by the present invention, obtains dry sediment.The present invention
There is no particular/special requirement to the washing and dry specific embodiment, is washed using material well-known to those skilled in the art
With drying mode.
After obtaining sediment, the present invention preferably mixes the sediment with lithium source, carries out high temperature sintering, obtains lithium ion
Battery nucleocapsid positive electrode Li2SiO3@LiMn2-xMxO4.In the present invention, the lithium source preferably includes lithium carbonate, lithium hydroxide
With one of lithium acetate or a variety of.In the present invention, the amount of the substance of the lithium source be preferably the amount of silicon source substance 2.0~
2.1 times, silicon source is with the content meter of silicon, and lithium source is with the content meter of lithium.Sediment and the mixture of lithium source are carried out high temperature by the present invention
Sintering, obtains lithium ion battery nucleocapsid positive electrode.In the present invention, the temperature of the high temperature sintering is 700~900 DEG C, excellent
It is selected as 750~850 DEG C, further preferably 780~800 DEG C；The time of the high temperature sintering is 3~10h, preferably 4~6h.
In the present invention, the temperature of the high temperature sintering is preferably reached in a manner of heating；The rate of the heating is preferably 3~6 DEG C/
Min, further preferably 3.5~5 DEG C/min.
When the fast-ionic conductor clad is La in chemical composition0.7Sr0.3Mn0.7Co0.3O3When, the fast ion is led
The in-situ synthetic method of body clad preferably includes：
Lanthanum nitrate, strontium nitrate, manganese nitrate and cobalt nitrate are dissolved in the water, citric acid is added, obtains reaction material liquid；
The pH value for adjusting the reaction material liquid using ammonium hydroxide obtains acid solution to 3~5；
By the acid solution and the LiMn2-xMxO4Nucleome is stirred, and obtains gel；
The gel is successively pre-sintered and is re-sintered, in core surface fabricated in situ La0.7Sr0.3Mn0.7Co0.3O3
Fast-ionic conductor clad.
In the present invention, in terms of lanthanum, strontium, manganese and cobalt, the acid lanthanum, strontium nitrate, the molar ratio of manganese nitrate and cobalt nitrate are excellent
It is selected as 0.7:0.3:0.7:0.3.In the present invention, the mole of the citric acid preferably with metal ion integral molar quantity phase
Deng；The citric acid plays the role of chelating agent so that metal ion in conjunction with chelator molecule, formed stable, metal from
The finely dispersed compound of son.
After obtaining reaction material liquid, present invention preferably employs ammonium hydroxide to adjust the pH value of the reaction material liquid to 3, obtains acid molten
Liquid.The present invention does not have particular/special requirement to the concentration and dosage of the ammonium hydroxide, to be able to achieve the adjustment to reaction material liquid pH value.
After obtaining acid solution, the present invention is preferably by the acid solution and the LiMn2-xMxO4Nucleome is stirred, and is obtained
To gel.In the present invention, the time being stirred is preferably 6h；The temperature being stirred is preferably 70 DEG C.
After obtaining gel, the gel is preferably successively pre-sintered and is re-sintered by the present invention, in core surface original position
Synthesize La0.7Sr0.3Mn0.7Co0.3O3Fast-ionic conductor clad.In the present invention, the temperature of the pre-sintering be preferably 400~
500 DEG C, the time of the pre-sintering is preferably 4~5h；The temperature re-sintered is preferably 700~900 DEG C, described to re-sinter
Time be preferably 10~15h.In core surface fabricated in situ fast-ionic conductor clad, primary core-shell material is obtained
La0.7Sr0.3Mn0.7Co0.3O3@LiMn1.95Mg0.05O4。
When the fast-ionic conductor clad is LaMnO in chemical composition3When, the original of the fast-ionic conductor clad
Position synthetic method preferably includes：
Lanthanum nitrate and manganese nitrate are dissolved in the water, citric acid is added, obtains reaction material liquid；
The pH value for adjusting the reaction material liquid using ammonium hydroxide obtains acid solution to 3~5；
By the acid solution and the LiMn2-xMxO4Nucleome is stirred, and obtains gel；
The gel is successively pre-sintered and is re-sintered, in core surface fabricated in situ LaMnO3Fast-ionic conductor packet
Coating.
In the present invention, the molar ratio of the lanthanum nitrate and manganese nitrate is preferably 1:1.In the present invention, the citric acid
Mole it is preferably equal with metal ion integral molar quantity；The citric acid plays the role of chelating agent so that metal ion with
Chelator molecule combines, and forms stable, the finely dispersed compound of metal ion.
After obtaining reaction material liquid, the pH value for adjusting the reaction material liquid present invention preferably employs ammonium hydroxide obtains acid to 3~5
Property solution.The present invention does not have particular/special requirement to the concentration and dosage of the ammonium hydroxide, to be able to achieve the adjustment to reaction material liquid pH value
?.
After obtaining acid solution, the present invention is preferably by the acid solution and the LiMn2-xMxO4Nucleome is stirred, and is obtained
To gel.In the present invention, the time being stirred is preferably 4h；The temperature being stirred is preferably 70 DEG C.
After obtaining gel, the gel is preferably successively pre-sintered and is re-sintered by the present invention, in core surface original position
Synthesize La0.7Sr0.3Mn0.7Co0.3O3Fast-ionic conductor clad.In the present invention, the temperature of the pre-sintering be preferably 400~
500 DEG C, the time of the pre-sintering is preferably 4~5h；The temperature re-sintered is preferably 700~900 DEG C, described to re-sinter
Time be preferably 10~15h.In core surface fabricated in situ fast-ionic conductor clad, primary core-shell material is obtained
LaMnO3@LiMn1.95Mg0.05O4。
After obtaining primary core-shell material, the present invention is in the primary core-shell material surface in situ synthesis electronic conductor cladding
Layer, obtains manganate cathode material for lithium.
In the present invention, when the electronic conductor clad of fabricated in situ is polypyrrole clad, the fabricated in situ
Mode includes：
The primary core-shell material is added in the ethanol solution containing pyrrole monomer and toluenesulfonic acid sodium salt, is obtained suspended
Liquid；
The suspension and ferric salt solution are mixed, oxidative polymerization is carried out.
The primary core-shell material is preferably added to the ethanol solution containing pyrrole monomer and toluenesulfonic acid sodium salt by the present invention
In, obtain suspension.In the present invention, the dosage of the pyrrole monomer is LiMn to be converted into the meter of polyaniline2-xMxO4Core
The 0.5%~2.2% of weight, further preferably 1.0%~2.0%；The quality of the pyrrole monomer and toluenesulfonic acid sodium salt
Than being preferably 3：1；The present invention to the dosage of the ethyl alcohol do not have it is special to go, to be able to achieve to pyrrole monomer and toluenesulfonic acid sodium salt
Abundant dissolution.
In the present invention, the primary core-shell material is preferably added under the conditions of magnetic agitation, so that each component dispersion is equal
It is even.In the present invention, the toluenesulfonic acid sodium salt plays the role of dopant.
After obtaining suspension, the present invention preferably mixes the suspension and ferric salt solution, and it is anti-to carry out oxidation polymerization
It answers, in primary core-shell material core surface in situ synthesis of polypyrrole clad.Concentration of the present invention to the ferric salt solution
There is no particular/special requirement, using well-known to those skilled in the art.In the present invention, trivalent in the ferric salt solution
Iron ion and the amount of the substance of pyrrole monomer are preferably equal.In the present invention, the time of the oxidative polymerization be preferably 5~
10h, the iron salt solutions polymerize the pyrroles in suspension as oxidant, so that electronic conductor fills up core surface
The incomplete position of fast-ionic conductor clad also further forms electronic conductor clad in fast-ionic conductor cover surface.
In the present invention, when the electronic conductor clad of the fabricated in situ is polyaniline-coated layer, the conjunction in situ
At mode include：
Aniline is added after the primary core-shell material is dispersed in water, obtains dispersion feed liquid；
The pH value for adjusting the dispersion feed liquid using hydrochloric acid obtains acid solution to 3~5；
The acid solution is mixed with ammonium persulfate, under the conditions of ice-water bath, carries out cladding precipitating.
Aniline is added after being preferably dispersed in water the primary core-shell material in the present invention, obtains dispersion feed liquid.In this hair
In bright, the dosage of the aniline is LiMn to be converted into the meter of polyaniline2-xMxO4The 0.5%~2.2% of nucleome quality, into
One step is preferably 1.0%~2.0%.The present invention does not have particular/special requirement to the dosage of the water, to be able to achieve to core-shell material and
The dispersing and dissolving of aniline.
After obtaining dispersion feed liquid, present invention preferably employs hydrochloric acid to adjust the pH value for dispersing feed liquid to 4, obtains acid molten
Liquid.The present invention does not have particular/special requirement to the concentration and dosage of the hydrochloric acid, and the pH value for dispersing feed liquid is adjusted to target value i.e.
It can.
The present invention preferably mixes the acid solution with ammonium persulfate, under the conditions of ice-water bath, carries out cladding precipitating.?
In the present invention, the cladding precipitating preferably carries out under nitrogen protection, and the time of the cladding precipitating is preferably 6~8h.This hair
Bright ammonium persulfate plays the role of oxidant under the pH value condition, and aniline is promoted to polymerize, and forms polyaniline electronics and leads
Body clad, so that electronic conductor fills up the incomplete position of core surface fast-ionic conductor clad, also further in fast ion
Conductor cover surface forms electronic conductor clad.
The present invention is on the basis of core surface coats fast-ionic conductor, then carrying out the cladding of electronic conductor on the one hand can be with
The complete cladding for largely realizing fertile material surface, on the other hand can improve lithium ion diffusivity and electronics simultaneously
Conductivity.
After the fabricated in situ for completing the electronic conductor clad, reaction material liquid is preferably successively filtered by the present invention,
Solid washing and drying, obtain manganate cathode material for lithium.The present invention is washed to the filtering, solid and dry specific embodiment party
Formula does not have particular/special requirement, using mode well-known to those skilled in the art.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to lithium ion battery mangaic acid provided by the invention
Lithium anode material and preparation method thereof is described in detail, but they cannot be interpreted as to the limit to the scope of the present invention
It is fixed.
Embodiment 1
Lithium ion battery mangaic acid lithium anode material is prepared according to flow chart shown in FIG. 1：By magnesium nitrate, electrolytic manganese dioxide
And lithium carbonate is 1.05 according to the molar ratio of Li, Mn and Mg：1.95:0.05 mixing, in the effect of dehydrated alcohol grinding aid
Lower simultaneously wet ball grinding 3 hours.After to ball milling, obtained mixed slurry is transferred in evaporating dish and is dried.Finally, will
Dry mixture grinding is uniformly placed on 450 DEG C pre-burning 4 hours in Muffle furnace, and regrinding is placed in Muffle furnace 780 DEG C
It burns eventually 15 hours and obtains LiMn1.95Mg0.05O4。
Molar ratio according to lanthanum, strontium, manganese and cobalt is 0.7:0.3:0.7:0.3, by lanthanum nitrate, strontium nitrate, manganese nitrate and
Cobalt nitrate is dissolved in 50 DEG C of deionized water, is added and the citric acid of metal ion equimolar amounts is as chelating agent, and dropwise
It is 3 that ammonium hydroxide, which is added, and adjusts the pH value of solution.Then, solution is warming up to 70 DEG C, the LiMn of 10g is added1.95Mg0.05O4, and continue
Stirring forms gel；Again to gel drying processing after, be first placed at 400 DEG C pre-burning 5 hours and burnt 10 hours eventually at 700 DEG C,
Obtain primary nuclei shell material La0.7Sr0.3Mn0.7Co0.3O3@LiMn1.95Mg0.05O4。
Then dopant paratoluenesulfonic acid sodium salt and 0.15g pyrrole monomer are dispersed in dehydrated alcohol (pyrrole monomer
Molar ratio with paratoluenesulfonic acid sodium salt is 3：1) above-mentioned primary core-shell material, and under conditions of continuing magnetic force stirring is added, obtains
To suspension；Then by the oxidant FeCl with pyrrole monomer equimolar amounts3·6H2O is added dropwise in above-mentioned suspension, is held
Continuous stirring 6h completes oxidation polymerization process, completes the cladding of electronic conductor clad.
Suspension obtained above is filtered, is washed and drying process obtains target material PPy/
La0.7Sr0.3Mn0.7Co0.3O3@LiMn1.95Mg0.05O4.Wherein, PPy, La0.7Sr0.3Mn0.7Co0.3O3And LiMn1.95Mg0.05O4's
Mass ratio is 1.5:1.5:100.
Constant current charge-discharge test is carried out to manganate cathode material for lithium manufactured in the present embodiment.According to test result, this is multiple
Close positive electrode specific discharge capacity with higher, excellent stable circulation performance, big high rate performance and high-temperature behavior.55
Under DEG C hot environment, when charge-discharge magnification is 0.5C, the first discharge specific capacity of the composite positive pole be can reach
126.2mAh/g still can reach 124.1mAh/g after recycling 200 times, and capacity retention ratio is up to 98.3%；It should be in 0.5C condition
Under high temperature cyclic performance curve graph as shown in Fig. 2, as shown in Figure 2, the positive electrode that the present embodiment obtains has excellent height
Warm cyclical stability.
Embodiment 2：
By aluminum nitrate, mangano-manganic oxide and lithium hydroxide according to Li, Mn and Al molar ratio be 1.05：1.95:0.05
Mixing, simultaneously wet ball grinding 3 hours under the action of dehydrated alcohol grinding aid.After to ball milling, the mixed slurry that will obtain
It is transferred in evaporating dish and is dried.Finally, it is small that dry mixture grinding is uniformly placed on 400 DEG C of pre-burnings 6 in Muffle furnace
When, regrinding is placed on 800 DEG C of whole burn 12 hours in Muffle furnace and obtains LiMn1.95Al0.05O4。
It is coated altogether to implement two-phase, by the LiMn of 10g1.95Al0.05O4Ultrasonic disperse is in dehydrated alcohol and deionized water
In mixed solution, then 0.35g ethyl orthosilicate is dissolved in dehydrated alcohol, then by the ethanol solution of ethyl orthosilicate
After mixing with the mixed solution of nucleome, ammonium hydroxide is added dropwise, generates precipitating.It (will be controlled after the washing drying of obtained sediment with lithium nitrate
The amount of the substance of lithium processed is 2.1 times of the amount of silicon matter in the cladding shell) it is uniformly mixed, it is placed in 750 DEG C of hot environment
High-temperature roasting 6h obtains primary core-shell material Li2SiO3@LiMn1.95Al0.05O4。
Then, it disperses above-mentioned primary core-shell material in suitable deionized water, the aniline of 0.15g is added, and continue
Stirring 30 minutes.Then, hydrochloric acid is added dropwise, the pH value for adjusting solution is 4, and the solution is transferred in ice-water bath.In nitrogen atmosphere
Under be added dropwise suitable ammonium persulfate, after reaction 6 hours, gained sediment is successively used deionized water, dehydrated alcohol and
Acetone repeatedly washs, and is dried in vacuo 10 hours under 80 DEG C of environment and obtains PANI/Li2SiO3@LiMn1.95Al0.05O4, wherein
PANI、Li2SiO3And LiMn1.95Al0.05O4Mass ratio be 1.5:1.5:100.
Constant current charge-discharge test is carried out to manganate cathode material for lithium manufactured in the present embodiment.According to test result, this is multiple
Close positive electrode specific discharge capacity with higher, excellent stable circulation performance, big high rate performance and high-temperature behavior.55
Under DEG C hot environment, when charge-discharge magnification is 0.5C, the first discharge specific capacity of the composite positive pole be can reach
126.8mAh/g still can reach 125.3mAh/g after recycling 200 times, and capacity retention ratio is up to 98.8%.
Embodiment 3：
By zinc acetate, manganese acetate and lithium acetate according to Li, Mn and Zn molar ratio be 1.05：1.95:0.05 mixing,
Simultaneously wet ball grinding 3 hours under the action of dehydrated alcohol grinding aid.After to ball milling, obtained mixed slurry is transferred to steaming
It is dried in hair ware.Finally, dry mixture grinding is uniformly placed on 450 DEG C pre-burning 4 hours in Muffle furnace, grind again
Mill is placed on 780 DEG C of whole burn 15 hours in Muffle furnace and obtains LiMn1.95Zn0.05O4。
It is 1 according to the molar ratio of lanthanum and manganese and cobalt:1, lanthanum nitrate and manganese nitrate are dissolved in 50 DEG C of deionized water, are added
Enter the citric acid with metal ion equimolar amounts as chelating agent, and it is 3 that ammonium hydroxide, which is added dropwise, to adjust the pH value of solution.Then,
Solution is warming up to 60 DEG C, the LiMn of 10g is added1.95Zn0.05O4, and continue stirring until and to form gel, then wet gel is placed in
Dry 12h under 110 DEG C of environment, gel is then first placed on at 400 DEG C pre-burning 4 hours and burnt eventually at 700 DEG C 10 hours to get
To primary core-shell material LaMnO3@LiMn1.95Zn0.05O4。
Then the pyrrole monomer of dopant paratoluenesulfonic acid sodium salt and 0.15g is dispersed in dehydrated alcohol (pyrroles's list
The molar ratio of body and paratoluenesulfonic acid sodium salt is 3：1) above-mentioned primary core-shell material, and under conditions of continuing magnetic force stirring is added,
Obtain suspension；Then by the oxidant FeCl with pyrrole monomer equimolar amounts3·6H2O is added dropwise in above-mentioned suspension,
Persistently stirring 6h completes oxidation polymerization process, completes the cladding of electronic conductor clad.
Suspension obtained above is filtered, is washed and drying process obtains target material PPy/LaMnO3@
LiMn1.95Zn0.05O4。
Constant current charge-discharge test is carried out to the manganate cathode material for lithium of preparation.According to test result, the anode composite material
Expect specific discharge capacity with higher, excellent stable circulation performance, big high rate performance and high-temperature behavior.In 55 DEG C of high temperature rings
Under border, when charge-discharge magnification is 0.5C, the first discharge specific capacity of the composite positive pole can reach 125.9mAh/g, circulation
Still it can reach 123.4mAh/g after 200 times, capacity retention ratio is up to 98.0%.
As seen from the above embodiment, manganate cathode material for lithium provided by the invention specific discharge capacity with higher, excellent
Stable circulation performance, high rate performance and high-temperature behavior；The present invention is using lower valency element doping to lithium manganate having spinel structure
It is modified, using modified LiMn2O4 as nucleome, while restrained effectively in material outside nucleome with two-phase clad
Mn3+The dissolution of Mn and the problems such as oxygen defect in material in the Jahn-Teller distortion effect of ion, electrolyte, significantly
Promotion while improving the structural stability of material, and taken into account material lithium ion diffusivity and electronic conductivity.The present invention
Cladding fast-ionic conductor clad and electronic conductor clad is laminated in nucleome material surface, can largely realize mother
Contact of the active material with electrolyte can be more efficiently isolated in the complete cladding of body material surface, effectively inhibit the molten of manganese
Solution；And lithium ion diffusivity can be improved simultaneously and electronic conductivity is effective；Furthermore two-phase coats altogether and lower valency doping association
It is modified with optimization, the long circulation life of material can be significantly increased using the syneryistic effect that the two generates.
Reaction raw material sources used in preparation process of the present invention are abundant, and inexpensively, production cost is low for price, is easy to
Scale business application.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of lithium ion battery mangaic acid lithium anode material, including chemical composition are LiMn2-xMxO4Nucleome and two-phase shell；0
X≤0.1 <；The M is lithium ion, positive bivalent metal ion or positive trivalent metal ion, and the positive bivalent metal ion includes
Magnesium ion, zinc ion or copper ion, positive trivalent metal ion include aluminium ion, cobalt ions or chromium ion；
The two-phase shell is the fast-ionic conductor clad and electronic conductor clad of stacking cladding, the fast-ionic conductor packet
Coating is coated on the core surface.
2. lithium ion battery mangaic acid lithium anode material according to claim 1, which is characterized in that fast in the two-phase shell
Ion conductor includes Li2SiO3、La0.7Sr0.3Mn0.7Co0.3O3、Li1.4Al0.4Ti1.6(PO4)3、Li3PO4Or LaMnO3, electronics leads
Body includes polypyrrole or polyaniline；
The mass ratio of fast-ionic conductor and electronic conductor is (0.5~2) in the two-phase shell：1.
3. lithium ion battery mangaic acid lithium anode material according to claim 1 or 2, which is characterized in that the two-phase shell
Quality be nucleome quality 1~5%.
4. a kind of preparation method of lithium ion battery mangaic acid lithium anode material, includes the following steps：
(1) mixed powder including lithium source, manganese source and doped source is provided；
The molar ratio of lithium source, manganese source and doped source is 1 in the mixed powder：[1.9,2)：(0,0.1]；
(2) mixed powder that the step (1) obtains successively is pre-sintered and is re-sintered, obtain LiMn2-xMxO4Nucleome；Institute
The temperature for stating pre-sintering is 400~450 DEG C, and the time of pre-sintering is 4~6h；The temperature re-sintered is 750~825 DEG C,
The time re-sintered is 12~18h；
(3) LiMn obtained in the step (2)2-xMxO4Core surface fabricated in situ fast-ionic conductor clad, obtains primary
Core-shell material；
(4) electronic conductor clad is synthesized in the primary core-shell material surface in situ that the step (3) obtains, is obtaining LiMn2O4 just
Pole material；
Doped source includes the oxidation of lithium salts, magnesium salts, zinc salt, mantoquita, aluminium salt, cobalt salt, chromic salts or respective metal in the step (1)
Object.
5. the preparation method according to claim 4, which is characterized in that the temperature that is pre-sintered in the step (2) and reburn
The temperature of knot is reached in a manner of heating up, and the rate of the heating independently is 3~6 DEG C/min.
6. the preparation method according to claim 4, which is characterized in that when the electronics of fabricated in situ in the step (4) is led
When body clad is polypyrrole clad, the mode of the fabricated in situ includes：
The primary core-shell material that the step (3) obtains is added to the ethanol solution containing pyrrole monomer and toluenesulfonic acid sodium salt
In, obtain suspension；
The suspension and ferric salt solution are mixed, oxidative polymerization is carried out.
7. the preparation method according to claim 4, which is characterized in that when the electronics of fabricated in situ in the step (4) is led
When body clad is polyaniline-coated layer, the mode of the fabricated in situ includes：
Aniline is added after the primary core-shell material that the step (3) obtains is dispersed in water, obtains dispersion feed liquid；
The pH value for adjusting the dispersion feed liquid using hydrochloric acid obtains acid solution to 3~5；
The acid solution is mixed with ammonium persulfate, under the conditions of ice-water bath, carries out cladding precipitating.
8. the preparation method according to claim 4, which is characterized in that lithium source includes lithium carbonate, hydrogen-oxygen in the step (1)
Change one of lithium and lithium acetate or a variety of；
The manganese source includes manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, hydroxyl manganese oxide, manganese acetate, manganese carbonate, nitric acid
One of manganese and manganese oxalate are a variety of.
9. the preparation method according to claim 4 or 8, which is characterized in that doped source is respective metal in the step (1)
Nitrate, acetate or oxide.
10. the preparation method according to claim 4, which is characterized in that the preparation method of mixed powder in the step (1)
Including：It is dried after lithium source, manganese source and doped source to be carried out to 3~8h of wet ball grinding in dehydrated alcohol, obtains drying composite；It will
The drying composite carries out dry grinding, obtains mixed powder.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109698346A (en) * | 2018-12-29 | 2019-04-30 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN109728285A (en) * | 2019-01-03 | 2019-05-07 | 清远佳致新材料研究院有限公司 | Anode material for lithium-ion batteries and preparation method thereof, lithium ion battery and electrical equipment |
| CN109920991A (en) * | 2019-03-07 | 2019-06-21 | 江西星盈科技有限公司 | Tertiary cathode material and preparation method thereof and lithium ion battery comprising the material |
| CN110931797A (en) * | 2019-12-09 | 2020-03-27 | 宁波容百新能源科技股份有限公司 | High-nickel positive electrode material with composite coating layer and preparation method thereof |
| CN111916702A (en) * | 2020-07-24 | 2020-11-10 | 惠州亿纬锂能股份有限公司 | Coated modified cathode material, preparation method thereof and lithium ion battery |
| CN112349905A (en) * | 2019-08-06 | 2021-02-09 | 湖南杉杉新能源有限公司 | Double-coating modified lithium ion battery positive electrode material and preparation method thereof |
| CN112897584A (en) * | 2021-01-21 | 2021-06-04 | 湘潭大学 | Lithium-rich manganese-based cathode material with divalent cations doped in lithium layer and preparation method thereof |
| CN113471414A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Lithium ion battery composite positive electrode material and preparation method and application thereof |
| CN115133020A (en) * | 2021-03-25 | 2022-09-30 | 宁德时代新能源科技股份有限公司 | Lithium manganate positive electrode active material, positive electrode plate comprising same, secondary battery, battery module, battery pack and electric device |
| WO2022252111A1 (en) * | 2021-06-01 | 2022-12-08 | 宁德时代新能源科技股份有限公司 | Lithium manganese oxide positive electrode active material, positive electrode plate containing same, secondary battery, battery module, battery pack and electrical device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
| CN103682356A (en) * | 2012-09-18 | 2014-03-26 | 华为技术有限公司 | Lithium ion battery anode material and preparation method thereof |
-
2018
- 2018-07-09 CN CN201810746039.6A patent/CN108878852A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
| CN103682356A (en) * | 2012-09-18 | 2014-03-26 | 华为技术有限公司 | Lithium ion battery anode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGYUAN ZHAO ET AL.: ""LiSixMn2-xO4(x≤0.10) cathode materials with improved electrochemical properties prepared via a simple solid-state method for high-performance lithium-ion batteries"", 《CERAMICS INTERNATIONAL》 * |
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Application publication date: 20181123 |