CN107240692A - A kind of spherical lithium manganate doped preparation method - Google Patents
A kind of spherical lithium manganate doped preparation method Download PDFInfo
- Publication number
- CN107240692A CN107240692A CN201710481031.7A CN201710481031A CN107240692A CN 107240692 A CN107240692 A CN 107240692A CN 201710481031 A CN201710481031 A CN 201710481031A CN 107240692 A CN107240692 A CN 107240692A
- Authority
- CN
- China
- Prior art keywords
- doped
- lithium manganate
- solution
- spherical
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of spherical lithium manganate doped preparation method, the spherical lithium manganate doped preparation method comprises the following steps：（1）The soluble manganese salt for weighing doped chemical soluble-salt and bivalent manganese is configured to the mixed solution of ion containing doped chemical and divalent manganesetion with water；（2）Sodium hydroxide solution is made；（3）Mixed solution and sodium hydroxide solution are continuously added in reactor, coprecipitation reaction is carried out, while enough oxidants are added into reaction solution carries out oxidation processes to sediment, is then rinsed with water, then through being dried to obtain spherical doping mangano-manganic oxide；（4）Weigh lithium carbonate or the spherical doping mangano-manganic oxide of lithium hydroxide is sufficiently mixed, be calcined in oxygen or air atmosphere high temperature, obtain spherical lithium manganate doped.Spherical lithium manganate doped impurity content prepared by the present invention is low, doped chemical molecular level is uniform, can solve the problem that the problem of LiMn2O4 cycle performance is poor.
Description
Technical field
The present invention relates to a kind of spherical lithium manganate doped preparation method, belong to field of lithium ion battery anode.
Background technology
The features such as lithium ion battery has high operating voltage, specific energy height, memory-less effect, in consumer digital product
（Smart mobile phone, notebook computer etc.）, the field such as electric automobile and energy-storage battery is applied.In recent years, with lithium-ion electric
Pool technology constantly improves, and electric automobile is fast-developing, wherein Tesla Model S, daily output Leaf, Chevrolet Volt, BYD
The electric cars such as E6 obtain good market sales volume, and the market demand of electrokinetic cell anode material for lithium-ion batteries also increases therewith
Plus.It is cobalt acid lithium to be commercialized most ripe positive electrode at present（LiCoO2）, it has preferable chemical property, but security
It is bad and expensive, it is not suitable for electrokinetic cell；Spinel lithium manganate（LiMn2O4）, LiFePO4（LiFePO4）, binary material
Material（LiNixCo1-xO2）And ternary material（LiNixCoyMn1-x-yO2）Deng being applied in electrokinetic cell.LiFePO4 is pacified
Quan Xinggao, have extended cycle life, but to there is uniformity bad for product, the problems such as pole piece processing characteristics and poor cryogenic property；Binary
Material, ternary material gram volume are high, but price is of a relatively high, security is poor；LiMn2O4 has raw material manganese rich reserves, cost
The good advantage of low, good rate capability, security, but cycle performance is poor, and particularly high temperature cyclic performance is poor, and constraining it should
With；LiMn2O4 cycle performance it is bad main reason is that, with the abjection and insertion of lithium in charge and discharge process, mangaic acid crystalline lithium
Structure constantly changes, and causes lattice stability reduction and manganese to dissolve in the electrolytic solution.
Current LiMn2O4 uses electrolytic manganese dioxide for manganese source mostly, by mixed with lithium carbonate or lithium hydroxide, additive
Close, be calcined and be made at high temperature, obtained LiMn2O4 performance is not good enough, and major defect is electrolytic manganese dioxide powder by machinery
Crushing is made, the bad control of its granule-morphology, usually indefinite form particle, and specific surface area is big；Other electrolytic manganese dioxide impurity
Content is high, and such as sulfate radical is generally more than 1.2%, calcium impurities in 300ppm or so, sodium impurity content 3000ppm level, and
Because plant equipment problem easily entrains iron tramp in crushing process, these factors are all adversely affected to LiMn2O4 performance.
It to improve LiMn2O4 structural stability, can be improved using doping modification method, be typically by lithium source, manganese source, mix
It is made after the compound mixing of miscellaneous element through high-temperature roasting, but this is likely to result in doped chemical skewness, main collection
In doping effect inside particle surface, particle cannot ensure.
The cycle performance for improving lithium manganate material, particularly high temperature cyclic performance are needed most at present, due to material purity
And the reason in terms of doping vario-property technique, still can not fundamentally solve the problem of LiMn2O4 cycle performance is poor.
The content of the invention
The technical problem to be solved in the present invention is：There is provided that a kind of impurity content is low, doped chemical molecular level is equally distributed
Spherical lithium manganate doped preparation method, this method can solve the problem that the problem of LiMn2O4 cycle performance is poor.
Solving the technical scheme of above-mentioned technical problem is：A kind of spherical lithium manganate doped preparation method, spherical doping manganese
The chemical formula of sour lithium is Li1+xMn2-yMy-xO4, wherein M is doped chemical, 0≤x≤0.1,0≤y-x≤0.5,
The spherical lithium manganate doped preparation method comprises the following steps：
（1）The soluble manganese salt for weighing doped chemical soluble-salt and bivalent manganese is configured to ion containing doped chemical and divalence with water
The mixed solution of manganese ion；In mixed solution, the concentration of divalent manganesetion is 20g/L~200g/L, doped chemical ion it is dense
Spend for 0.05g/L~50g/L,
（2）Sodium hydroxide is weighed, the sodium hydroxide solution that concentration is 50g/L~500g/L is configured to water；
（3）By above-mentioned steps（1）In mixed solution and step（2）In sodium hydroxide solution be continuously added to reactor
In, control the divalent manganesetion in reactor to be with the total mole number of doped chemical ion and the mole ratio of sodium hydroxide（0.5~
1.5）: 2, coprecipitation reaction is carried out, controlling reaction temperature is 40 DEG C~80 DEG C, the pH value of reaction solution is 7.5~13.5, while to
Enough oxidants are added in reaction solution oxidation processes are carried out to the sediment generated in course of reaction, then rinsed and separated with water
Sediment afterwards, then through being dried to obtain spherical doping mangano-manganic oxide；Described oxidant is hydrogen peroxide, oxygen, air, over cure
At least one of sour ammonium or sodium thiosulfate；
（4）Lithium carbonate or lithium hydroxide and step are weighed by the stoichiometric proportion in chemical formula（3）Four oxygen of obtained spherical doping
Change three manganese to be sufficiently mixed, then obtain ball through 700 DEG C~1000 DEG C high-temperature roastings 5~30 hours in oxygen or air atmosphere
Shape adulterated lithium manganate；
In step（1）Blender A is added in obtained mixed solution or in step（2）Added in obtained sodium hydroxide solution
Blender B or both in step（1）Blender A is added in obtained mixed solution, and in step（2）Obtained sodium hydroxide is molten
Blender B is added in liquid；The blender A is Si Ben -80, OP-10, lauryl sodium sulfate, ammonium fluoride, ammonium chloride, sulfuric acid
Ammonium, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropanol, n-butanol, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, second two
At least one of the sodium of amine tetraacethyl four, carboxymethyl cellulose, sodium carboxymethylcellulose and polyvinyl alcohol；The blender B bags
Include Si Ben -80, OP-10, lauryl sodium sulfate, ammoniacal liquor, ethylenediamine, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, fluorination
Sodium, ethanol, ethylene glycol, isopropanol, n-butanol, EDTA, EDTA disodium, the sodium of EDTA tetra-, carboxymethyl cellulose, carboxymethyl cellulose
At least one of plain sodium and polyvinyl alcohol；Add after blender A, blender A concentration is controlled in 0.1g/L in mixed solution
~20g/L, is added after blender B, and blender B concentration is controlled in 0.1g/L~50g/L in sodium hydroxide solution.
M is at least one of Li, Ni, Mg, Al, Co, Cr, Ti element in chemical formula.
Step（4）In sintering temperature be 800~900 DEG C, roasting time be 10~30 hours.
Step（1）Described in soluble manganese salt at least one of for manganese sulfate, manganese nitrate and manganese chloride.
Step（1）Described in doped chemical soluble-salt at least one of for sulfate, nitrate and chlorate.
The present invention further technical scheme be：Enough oxidants are added into reaction solution to generating in course of reaction
Sediment carry out oxidation processes concrete operation step be：It is that 5~15% oxidants carry out oxygen that mass concentration is added into reaction solution
Change processing 5~20 hours, the consumption of oxidant is to control the pH value of reaction solution to be defined for 7.5~13.5, and described oxidant is
At least one of hydrogen peroxide, ammonium persulfate solution and hypo solution.
Compared with prior art, the advantage of the invention is that：The technological process of preparation method of the present invention is simple, it is easy to accomplish
Large-scale production；In the present invention, impurity content is prepared by wet processing first low, the equally distributed ball of doped chemical molecular level
Shape doping mangano-manganic oxide presoma, is then prepared spherical lithium manganate doped using spherical doping mangano-manganic oxide as manganese source.Can
The impurity content of product is reduced by controlling the impurity level of raw material, microstructure is produced for spherical powder particle,
Realize the Uniform Doped effect of molecular level.The spherical lithium manganate doped product produced using the inventive method, with vertical
Square spinel structure, space group Fd-3m（No.227）Lithium manganate particle；Its impurity content is low, and potassium, sodium, calcium impurities content are equal
Less than 50ppm, iron, copper impurity content are less than 20ppm, and sulfate radical content is less than 0.1%；Doped chemical is inside lithium manganate particle
It is uniformly distributed for molecular level, it is possible to increase LiMn2O4 structural stability；Its microcosmic second particle pattern is spherical, granularity D50For 5 μ
M~20 μm；Specific surface area is less than 0.8m2/ g, tap density is more than 2.0g/cm3；Through 55 DEG C of high temperature circulations 200 times, capacity is kept
Rate is more than 95%, can significantly improve the cycle performance of LiMn2O4, particularly high temperature cyclic performance, and can strengthen LiMn2O4 in appearance
Application in amount type lithium ion battery and electrokinetic cell, is the preferable positive electrode of high-end lithium ion battery.
With by lithium source, manganese source（Manganese oxide, manganous hydroxide or manganese carbonate）With high-temperature roasting after doped compound solid phase mixing
The traditional handicraft for preparing LiMn2O4 is compared, and impurity content of the present invention is lower, and doped chemical is more evenly distributed inside particle；With it is wet
Method prepares manganese oxide, manganous hydroxide or manganese carbonate presoma, then high temperature after the mixing of manganese presoma, lithium source and doped compound is roasted
The technique for firing standby LiMn2O4 is compared, and doped chemical of the present invention is more evenly distributed inside particle；Manganese oxide, hydrogen are prepared with wet method
Manganese oxide or manganese carbonate, on its surface, precipitation doping element compound obtains the manganese presoma that adulterates, then by before lithium source and doping manganese
Drive high-temperature roasting after body mixing and prepare the technique of LiMn2O4 and compare, doped chemical of the present invention is more evenly distributed inside particle.
Brief description of the drawings
Fig. 1 is obtained spherical lithium manganate doped XRD diffraction patterns in the embodiment of the present invention 1.
Fig. 2 is obtained spherical lithium manganate doped SEM figures in the embodiment of the present invention 1.
Fig. 3 is obtained spherical lithium manganate doped SEM figures in the embodiment of the present invention 4.
Fig. 4 is obtained spherical lithium manganate doped cyclic curve figure in the embodiment of the present invention 1.
Embodiment
A kind of spherical lithium manganate doped preparation method, spherical lithium manganate doped chemical formula is Li1+xMn2-yMy-xO4, its
Middle M is doped chemical, and M is at least one of elements such as Li, Ni, Mg, Al, Co, Cr, Ti, 0≤x≤0.1,0≤y-x≤
0.5.Spherical lithium manganate doped is with cubic spinel structure, space group Fd-3m（No.227）Lithium manganate particle；Its impurity
Content is low, and potassium, sodium, calcium impurities content are respectively less than 50ppm, and iron, copper impurity content are less than 20ppm, and sulfate radical content is less than 0.1%；
Doped chemical is uniformly distributed inside lithium manganate particle for molecular level, it is possible to increase structural stability；Its microcosmic second particle shape
Looks are spherical, granularity D50For 5 μm~20 μm；Specific surface area is less than 0.8m2/ g, tap density is more than 2.0g/cm3。
The spherical lithium manganate doped preparation method comprises the following steps：
（1）By the stoichiometric proportion in chemical formula weigh doped chemical soluble-salt and bivalent manganese soluble manganese salt pure water or
Deionized water is configured to the mixed solution of ion containing doped chemical and divalent manganesetion；In mixed solution, divalent manganesetion it is dense
Spend for 20g/L~200g/L, the concentration of doped chemical ion is 0.05g/L~50g/L, and soluble manganese salt is manganese sulfate, nitric acid
At least one of manganese, manganese chloride, for example, can be one kind in foregoing soluble manganese salt or wherein any two manganese
The mixing of the arbitrary proportion of salt, can also be the mixing of wherein three kinds of arbitrary proportion.Doped chemical soluble-salt be sulfate,
At least one of nitrate, chlorate.It for example can be one kind in abovementioned dopant element soluble-salt or wherein
The mixing of any two kinds of arbitrary proportion, can also be the mixing of wherein three kinds of arbitrary proportion.
（2）Blender A is weighed, step is added it to（1）In obtained mixed solution, it is mixing uniformly to form containing mediation
Agent A concentration is 0.1g/L~20g/L mixed solution；Blender A is Si Ben -80, OP-10, lauryl sodium sulfate, fluorination
Ammonium, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropanol, n-butanol, EDTA, EDTA disodium, EDTA
At least one of four sodium, carboxymethyl cellulose, sodium carboxymethylcellulose and polyvinyl alcohol（According to blender B service condition,
Blender A can be not added with）；In the manganese salt solution of preparation, if precipitation or impurity, it is necessary to first be filtered or removal of impurities processing,
It is to carry out removal of impurities processing to raw material before preparation to go deimpurity preferably opportunity.
（3）Sodium hydroxide is weighed, the sodium hydroxide that concentration is 50g/L~500g/L is configured to pure water or deionized water molten
Liquid（Sodium hydroxide used can be commercially available solid piece alkali, directly can also be prepared with commercially available liquid caustic soda）.
（4）Blender B is weighed, step is added it to（3）In obtained sodium hydroxide solution, it is mixing uniformly to form and contains
Blender B concentration is 0.1g/L~50g/L sodium hydroxide solution；Blender B is Si Ben -80, OP-10, dodecyl sulphur
Sour sodium, ammoniacal liquor, ethylenediamine, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropanol, positive fourth
At least one of alcohol, EDTA, EDTA disodium, the sodium of EDTA tetra-, carboxymethyl cellulose, sodium carboxymethylcellulose and polyvinyl alcohol
（Blender B can be optionally not added with）；The sodium hydroxide solution of preparation or the sodium hydroxide solution added after blender B, if
Precipitation or impurity, it is necessary to filtered after preparation or removal of impurities processing, to make the impurity content of final products minimum, be preferably exist
Removal of impurities processing is carried out to raw material before preparing.
（5）By above-mentioned steps（2）In mixed solution and step（4）In sodium hydroxide solution be continuously added to reaction
In device（While being proportionally added into while reaction）, divalent manganesetion and doped chemical ion is total in control reactor
The mole ratio of molal quantity and sodium hydroxide is（0.5~1.5）: 2, carry out coprecipitation reaction, controlling reaction temperature be 40 DEG C~
80 DEG C, the pH values of reaction solution are 7.5~13.5, while adding enough oxidants into reaction solution to being generated in course of reaction
Sediment carry out oxidation processes, make manganous compound precipitation be converted into mangano-manganic oxide；When course of reaction is continuous charging,
Overfall discharge on reaction product autoreactor；Then with the sediment after pure water or deionized water rinsing separation, then through dry
It is dry to obtain spherical doping mangano-manganic oxide；Described oxidant is hydrogen peroxide, oxygen, air, ammonium persulfate or sodium thiosulfate
At least one of；The consumption of oxidant cannot be below the theoretical requirement of reaction.
（6）Lithium carbonate or lithium hydroxide and step are weighed by the stoichiometric proportion in chemical formula（5）Obtained spherical doping
Mangano-manganic oxide is sufficiently mixed, and is then obtained in oxygen or air atmosphere through 700 DEG C~1000 DEG C high-temperature roastings 5~30 hours
To spherical lithium manganate doped.
Above-mentioned blender A and/or blender B effect is all easy for subsequent step（5）In precipitation be grown to ball
Can be to change the direction of growth of precipitation particle by selective absorption or by changing precipitation in shape, mechanism
Grain improves the speed of growth of crystal grain with the boundary moisture performance of reaction solution, can also be influence reaction speed to control precipitation
The speed of growth of grain；No matter for blender A and/or blender B, if the dissolution velocity from material is slow, it can carry out
Heat to accelerate dissolving.
For detection the present invention spherical lithium manganate doped physical and chemical performance, with French JY companies ULTIMA inductives etc. from
Sub- emission spectrometer（ICP-AES）Quantitative analysis is carried out to impurities of materials content；Use Dutch X ' Pert PRO-MPD type XRD diffraction
Instrument carries out structured testing；Granule-morphology is carried out with Japanese JEOL companies JSM-6360 LV types scanning electron microscope sems to analyze with size；
Grain size analysis is carried out with the type laser particle size analyzers of MALVERN Instrument Ltd. of Britain MASTERSIZER 2000；Use the U.S.
The NOVA-1000 types of Quantachrome companies carry out specific surface area analysis than Surface Tester.
For the spherical lithium manganate doped chemical property of the detection present invention, assemble them into CR2032 type button cells and enter
Row electrochemical property test, with the lithium manganate material 90% of the present invention（Percetage by weight）, conductive carbon black 5%, binding agent PVdF（It is poly-
Vinylidene）5%, mixing is tuned into pulpous state, is coated on aluminium foil, in 120 DEG C of dryings, electrode is made；Using metal lithium sheet as negative pole, electricity
Solution liquid is 1mol/L LiPF6/EC+DMC（Volume ratio 1:1）, EC is ethylene carbonate, and DMC is dimethyl carbonate, assembling
CR2032 type button cells.Charge-discharge test, 55 DEG C of test temperature, charging/discharging voltage are carried out with the blue electric battery test system in Wuhan
Scope is 3.0~4.3V, and first charge-discharge test multiplying power is 0.2C, and the 2nd time~the 201st time circulation is filled for 0.5C constant current constant voltages
Electricity, 1C constant-current discharges.
With reference to specific embodiment, the invention will be further described.
Embodiment 1：
A kind of of the invention spherical lithium manganate doped, its chemical formula is Li1.05Mn1.80Al0.15O4。
It is the manganese sulfate and sulfuric acid that 60g/L is 2.5g/L with trivalent aluminium ion concentration that divalent manganesetion concentration is prepared with pure water
Aluminium mixed solution 20L, weighs 60g isopropanols and 70g sodium fluorides are added in above-mentioned solution and stirred；Prepare dense with pure water
The sodium hydroxide solution 20L for 200g/L is spent, by manganese sulfate and aluminum sulfate mixture solution 500mL/h flow, manganese ion and aluminium
The ratio between the molal quantity sum of ion and the molal quantity of sodium hydroxide are 1: 2 ratio, with measuring pump by mixed solution and hydroxide
Sodium solution is added to volume in 10L reactor, to control the temperature of reaction to be 70 DEG C, and the pH values of reaction solution are 10.0, simultaneously
Logical enough air are aoxidized to precipitation, and reaction stops after carrying out 30 hours, washing, dry after, obtain mixing the oxidation of aluminium four three
Manganese presoma.Gained mixes aluminium mangano-manganic oxide granularity D50For 17.36 μm, tap density is 2.6 g/cm3。
By above-mentioned spherical aluminum-doped manganous-manganic oxide, lithium carbonate with Mn：Li mol ratio=1.80：1.05 ratio is weighed, fully
After mixing LiMn2O4 product is obtained in air atmosphere through 820 DEG C of high-temperature roastings 15 hours.
The defects inspecting result of gained LiMn2O4 is potassium 6ppm, sodium 38ppm, calcium 42ppm, iron 8ppm, copper 3ppm, sulfate radical
0.08%；Fig. 1 is XRD diffraction patterns, and gained LiMn2O4 does not have dephasign；Fig. 2 schemes for SEM, and gained LiMn2O4 second particle pattern is ball
Shape；Its granularity D50For 18.58 μm, specific surface area is 0.41 m2/ g, tap density is 2.1 g/cm3。
Using the LiMn2O4 of gained as positive active material, button cell is made, 55 DEG C of high temperature tests are carried out.Fig. 4 follows for it
Ring curve, as illustrated, 0.2C discharges gram volume for 106.6 mAh/g first, the 2nd time circulation 1C electric discharge gram volumes are 105.9
Capability retention is 95.4% after mAh/g, 1C are circulated 200 times.
Embodiment 2：
A kind of of the invention spherical lithium manganate doped, its chemical formula is Li1.05Mn1.85Al0.10O4。
It is the manganese sulfate and sulfuric acid that 60g/L is 1.6g/L with trivalent aluminium ion concentration that divalent manganesetion concentration is prepared with pure water
Aluminium mixed solution 20L, weighs 60g isopropanols and 70g sodium fluorides are added in above-mentioned solution and stirred；Prepare dense with pure water
The sodium hydroxide solution 20L for 200g/L is spent, by manganese sulfate and aluminum sulfate mixture solution 500mL/h flow, manganese ion and aluminium
The ratio between the molal quantity sum of ion and the molal quantity of sodium hydroxide are 1: 2 ratio, with measuring pump by mixed solution and hydroxide
Sodium solution is added to volume as in 10L reactor, the pH values of reaction solution are 10.0, and the temperature for controlling reaction is 70 DEG C, simultaneously
Add mass concentration to aoxidize precipitation for 10% hydrogen peroxide, the consumption of hydrogen peroxide is to control the pH of oxidizing process reaction solution
Be worth and be advisable for 9.5~10.5, reaction carry out 5 hours after stop, washing, dry after, obtain mixing aluminium mangano-manganic oxide presoma.Institute
What is obtained mixes aluminium mangano-manganic oxide granularity D50For 17.15 μm, tap density is 2.6 g/cm3。
By above-mentioned spherical aluminum-doped manganous-manganic oxide, lithium carbonate with Mn：Li mol ratio=1.85：1.05 ratio is weighed, fully
After mixing LiMn2O4 product is obtained in air atmosphere through 820 DEG C of high-temperature roastings 15 hours.
The defects inspecting result of gained LiMn2O4 is potassium 7ppm, sodium 42ppm, calcium 40ppm, iron 9ppm, copper 2ppm, sulfate radical
0.06%；Granularity D50For 18.03 μm, specific surface area is 0.45m2/ g, tap density is 2.1 g/cm3.55 DEG C of high temperature tests, it is first
Secondary 0.2C electric discharges gram volume is 113.1 mAh/g, and the 2nd time circulation 1C electric discharge gram volumes are 112.7 mAh/g, 1C high temperature circulations
Capability retention is 95.1% after 200 times.
Embodiment 3：
A kind of of the invention spherical lithium manganate doped, its chemical formula is Li1.06Mn1.84Co0.05Al0.05O4。
With pure water preparation divalent manganesetion concentration be 75g/L, divalent cobalt ion concentration is 2.2g/L and trivalent aluminium ion is dense
The manganese sulfate for 1.0g/L, cobaltous sulfate and aluminum sulfate mixture solution 20L are spent, 80g absolute ethyl alcohols is weighed and is added in above-mentioned solution
And stir；The sodium hydroxide solution 20L for being 120g/L with pure water compound concentration, weighs the ammoniacal liquor that mass fraction is 25%
300g is added in sodium hydroxide solution and stirred, by the stream of manganese sulfate, cobaltous sulfate and aluminum sulfate mixture solution 800mL/h
Measure, the ratio between molal quantity of manganese ion, cobalt ions and aluminum ions molal quantity sum and sodium hydroxide is 1: 2 ratio, with metering
Pump adds mixed solution and sodium hydroxide solution to volume in 10L reactor, to control the temperature of reaction to be 65 DEG C, reaction
The pH values of liquid are 9.5, precipitation are aoxidized for 10% hypo solution while adding mass concentration, sodium thiosulfate
The consumption of solution is to control the pH value of oxidizing process reaction solution to be advisable as 9~10, and reaction stops after carrying out 8 hours, washes, dries
Afterwards, obtain mixing cobalt aluminium mangano-manganic oxide presoma.Gained mixes cobalt aluminium mangano-manganic oxide granularity D50For 7.17 μm, tap density is
2.3 g/cm3。
By above-mentioned spherical cobalt aluminium mangano-manganic oxide, the lithium hydroxide mixed with Mn：Li mol ratio=1.84：1.06 ratio is weighed,
After being sufficiently mixed LiMn2O4 product is obtained in oxygen atmosphere through 850 DEG C of high-temperature roastings 15 hours.
The defects inspecting result of gained LiMn2O4 is potassium 2ppm, sodium 46ppm, calcium 42ppm, iron 10ppm, copper 2pm, sulfate radical
0.07%；Granularity D50For 8.71 μm, specific surface area is 0.56 m2/ g, tap density is 2.6 g/cm3；55 DEG C of high temperature tests, it is first
Secondary 0.2C electric discharges gram volume is 110.5 mAh/g, and the 2nd time circulation 1C electric discharge gram volumes are 110.0 mAh/g, 1C high temperature circulations
Capability retention is 95.3% after 200 times.
Embodiment 4：
A kind of of the invention spherical lithium manganate doped, its chemical formula is Li1.03Mn1.89Co0.05Ni0.03O4。
With pure water preparation divalent manganesetion concentration be 60g/L, divalent cobalt ion concentration is 1.7g/L and bivalent nickel ion is dense
Spend the manganese chloride for 1.0g/L, cobalt chloride and nickel chloride mixed solution 30L；The sodium hydroxide for being 180g/L with pure water compound concentration
Solution 30L, weighs 120g ammonium chlorides and 80g sodium fluoride are added in sodium hydroxide solution and stirring and dissolving is complete, by chlorination
The flow of manganese, cobalt chloride and nickel chloride mixed solution 700mL/h, the molal quantity sum and hydrogen of manganese ion, cobalt ions and nickel ion
The ratio between molal quantity of sodium oxide molybdena is 1: 2 ratio, is added mixed solution and sodium hydroxide solution to volume with measuring pump and is
In 10L reactor, the temperature for controlling reaction is 55 DEG C, and the pH values of reaction solution are 9.2, while it is 10% to add mass concentration
Ammonium persulfate solution is aoxidized to precipitation, the consumption of ammonium persulfate solution using control the pH value of oxidizing process reaction solution as 9~
10 are advisable, reaction carry out 10 hours after stop, washing, dry after, obtain mixing cobalt nickel mangano-manganic oxide presoma.Gained mixes cobalt
Nickel mangano-manganic oxide granularity D50For 9.08 μm, tap density is 2.4 g/cm3。
By above-mentioned spherical cobalt nickel mangano-manganic oxide, the lithium hydroxide mixed with Mn：Li mol ratio=1.89：1.03 ratio is weighed,
After being sufficiently mixed LiMn2O4 product is obtained in air atmosphere through 810 DEG C of high-temperature roastings 20 hours.
The defects inspecting result of gained LiMn2O4 is potassium 3ppm, sodium 36ppm, calcium 37ppm, iron 17ppm, copper 6pm, sulfate radical
0.05%；Fig. 3 schemes for SEM, and gained LiMn2O4 second particle pattern is spherical, granularity D50For 11.21 μm；Specific surface area is 0.51
m2/ g, tap density is 2.0 g/cm3；55 DEG C of high temperature tests, the 0.2C gram volumes that discharge are 116.1 mAh/g first, are followed for the 2nd time
Ring 1C electric discharge gram volumes are that capability retention is 95.4% after 115.5 mAh/g, 1C high temperature circulations 200 times.
Claims (6)
1. a kind of spherical lithium manganate doped preparation method, it is characterised in that：Spherical lithium manganate doped chemical formula is Li1+ xMn2-yMy-xO4, wherein M is doped chemical, 0≤x≤0.1,0≤y-x≤0.5,
The spherical lithium manganate doped preparation method comprises the following steps：
（1）The soluble manganese salt for weighing doped chemical soluble-salt and bivalent manganese is configured to ion containing doped chemical and divalence with water
The mixed solution of manganese ion；In mixed solution, the concentration of divalent manganesetion is 20g/L~200g/L, doped chemical ion it is dense
Spend for 0.05g/L~50g/L,
（2）Sodium hydroxide is weighed, the sodium hydroxide solution that concentration is 50g/L~500g/L is configured to water；
（3）By above-mentioned steps（1）In mixed solution and step（2）In sodium hydroxide solution be continuously added to reactor
In, control the divalent manganesetion in reactor to be with the total mole number of doped chemical ion and the mole ratio of sodium hydroxide（0.5~
1.5）: 2, coprecipitation reaction is carried out, controlling reaction temperature is 40 DEG C~80 DEG C, the pH value of reaction solution is 7.5~13.5, while to
Enough oxidants are added in reaction solution oxidation processes are carried out to the sediment generated in course of reaction, then rinsed and separated with water
Sediment afterwards, then through being dried to obtain spherical doping mangano-manganic oxide；Described oxidant is hydrogen peroxide, oxygen, air, over cure
At least one of sour ammonium or sodium thiosulfate；
（4）Lithium carbonate or lithium hydroxide and step are weighed by the stoichiometric proportion in chemical formula（3）Four oxygen of obtained spherical doping
Change three manganese to be sufficiently mixed, then obtain ball through 700 DEG C~1000 DEG C high-temperature roastings 5~30 hours in oxygen or air atmosphere
Shape adulterated lithium manganate；
In step（1）Blender A is added in obtained mixed solution or in step（2）Added in obtained sodium hydroxide solution
Blender B or both in step（1）Blender A is added in obtained mixed solution, and in step（2）Obtained sodium hydroxide is molten
Blender B is added in liquid；The blender A is Si Ben -80, OP-10, lauryl sodium sulfate, ammonium fluoride, ammonium chloride, sulfuric acid
Ammonium, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropanol, n-butanol, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, second two
At least one of the sodium of amine tetraacethyl four, carboxymethyl cellulose, sodium carboxymethylcellulose and polyvinyl alcohol；The blender B bags
Include Si Ben -80, OP-10, lauryl sodium sulfate, ammoniacal liquor, ethylenediamine, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, fluorination
Sodium, ethanol, ethylene glycol, isopropanol, n-butanol, EDTA, EDTA disodium, the sodium of EDTA tetra-, carboxymethyl cellulose, carboxymethyl cellulose
At least one of plain sodium and polyvinyl alcohol；Add after blender A, blender A concentration is controlled in 0.1g/L in mixed solution
~20g/L, is added after blender B, and blender B concentration is controlled in 0.1g/L~50g/L in sodium hydroxide solution.
2. spherical lithium manganate doped preparation method according to claim 1, it is characterised in that：In chemical formula M be Li,
At least one of Ni, Mg, Al, Co, Cr, Ti element.
3. spherical lithium manganate doped preparation method according to claim 1 or 2, it is characterised in that：Step（4）In roasting
It is 800~900 DEG C to burn temperature, and roasting time is 10~30 hours.
4. spherical lithium manganate doped preparation method according to claim 1 or 2, it is characterised in that：Step（1）Described in
Soluble manganese salt at least one of for manganese sulfate, manganese nitrate and manganese chloride.
5. spherical lithium manganate doped preparation method according to claim 1 or 2, it is characterised in that：Step（1）Described in
Doped chemical soluble-salt at least one of for sulfate, nitrate and chlorate.
6. spherical lithium manganate doped preparation method according to claim 1 or 2, it is characterised in that：Add into reaction solution
Entering the concrete operation step that enough oxidants carry out oxidation processes to the sediment that is generated in course of reaction is：Into reaction solution
It is that 5~15% oxidants carry out oxidation processes 5~20 hours to add mass concentration, and the consumption of oxidant is to control the pH of reaction solution
It is worth and is defined for 7.5~13.5, described oxidant is at least one in hydrogen peroxide, ammonium persulfate solution and hypo solution
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710481031.7A CN107240692A (en) | 2017-06-22 | 2017-06-22 | A kind of spherical lithium manganate doped preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710481031.7A CN107240692A (en) | 2017-06-22 | 2017-06-22 | A kind of spherical lithium manganate doped preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107240692A true CN107240692A (en) | 2017-10-10 |
Family
ID=59986591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710481031.7A Withdrawn CN107240692A (en) | 2017-06-22 | 2017-06-22 | A kind of spherical lithium manganate doped preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107240692A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336016A (en) * | 2019-07-16 | 2019-10-15 | 中钢集团南京新材料研究院有限公司 | A kind of preparation method for mixing aluminium LiMn2O4 |
| CN112390292A (en) * | 2020-11-13 | 2021-02-23 | 贵州大龙汇成新材料有限公司 | Bulk phase doped manganous-manganic oxide and preparation method and application thereof |
| CN112875758A (en) * | 2021-01-25 | 2021-06-01 | 浙江中金格派锂电产业股份有限公司 | Preparation method of low-cost high-capacity lithium manganate precursor |
| CN113421998A (en) * | 2021-06-21 | 2021-09-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN113517439A (en) * | 2020-06-30 | 2021-10-19 | 高点(深圳)科技有限公司 | Doped lithium manganate and preparation method and application thereof |
| CN113582234A (en) * | 2021-08-11 | 2021-11-02 | 南方锰业集团有限责任公司 | Preparation method of battery-grade spheroidal manganese carbonate |
| CN113782746A (en) * | 2021-08-31 | 2021-12-10 | 深圳市泽塔电源系统有限公司 | Preparation process of lithium manganate composite material with ternary shell layer |
| CN113816430A (en) * | 2021-07-30 | 2021-12-21 | 高点(深圳)科技有限公司 | Preparation method of modified mangano-manganic oxide, product and application |
| CN114044539A (en) * | 2021-10-30 | 2022-02-15 | 湖南海利锂电科技股份有限公司 | Preparation method of high-cycle power type lithium manganate |
| CN115028201A (en) * | 2022-05-23 | 2022-09-09 | 荆门市格林美新材料有限公司 | Preparation method and application of spherical MnOOH |
| CN115611317A (en) * | 2022-11-10 | 2023-01-17 | 浙江格派钴业新材料有限公司 | Preparation method of precursor material of high-tap anion-cation doped manganous-manganic oxide |
| CN115724468A (en) * | 2022-11-21 | 2023-03-03 | 中钢天源股份有限公司 | Preparation method of pre-doped lithium manganate precursor material and product thereof |
| CN116759561A (en) * | 2023-08-14 | 2023-09-15 | 中冶长天国际工程有限责任公司 | Bulk phase doped and surface coated manganous-manganic oxide material |
| CN117105275A (en) * | 2023-10-23 | 2023-11-24 | 湘潭电化科技股份有限公司 | Spherical manganous-manganic oxide and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034977A (en) * | 2010-11-10 | 2011-04-27 | 湘西自治州兴湘科技开发有限责任公司 | Preparation method of positive-pole materials (lithium manganate and doped lithium manganate) of lithium ion battery |
| CN102544472A (en) * | 2011-12-31 | 2012-07-04 | 湖南汇通科技有限责任公司 | Spherical aluminum-doped manganous-manganic oxide and preparation method thereof |
-
2017
- 2017-06-22 CN CN201710481031.7A patent/CN107240692A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034977A (en) * | 2010-11-10 | 2011-04-27 | 湘西自治州兴湘科技开发有限责任公司 | Preparation method of positive-pole materials (lithium manganate and doped lithium manganate) of lithium ion battery |
| CN102544472A (en) * | 2011-12-31 | 2012-07-04 | 湖南汇通科技有限责任公司 | Spherical aluminum-doped manganous-manganic oxide and preparation method thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336016A (en) * | 2019-07-16 | 2019-10-15 | 中钢集团南京新材料研究院有限公司 | A kind of preparation method for mixing aluminium LiMn2O4 |
| CN113517439A (en) * | 2020-06-30 | 2021-10-19 | 高点(深圳)科技有限公司 | Doped lithium manganate and preparation method and application thereof |
| CN112390292A (en) * | 2020-11-13 | 2021-02-23 | 贵州大龙汇成新材料有限公司 | Bulk phase doped manganous-manganic oxide and preparation method and application thereof |
| CN112875758A (en) * | 2021-01-25 | 2021-06-01 | 浙江中金格派锂电产业股份有限公司 | Preparation method of low-cost high-capacity lithium manganate precursor |
| CN113421998A (en) * | 2021-06-21 | 2021-09-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN113421998B (en) * | 2021-06-21 | 2022-07-08 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN113816430A (en) * | 2021-07-30 | 2021-12-21 | 高点(深圳)科技有限公司 | Preparation method of modified mangano-manganic oxide, product and application |
| CN113582234A (en) * | 2021-08-11 | 2021-11-02 | 南方锰业集团有限责任公司 | Preparation method of battery-grade spheroidal manganese carbonate |
| CN113782746A (en) * | 2021-08-31 | 2021-12-10 | 深圳市泽塔电源系统有限公司 | Preparation process of lithium manganate composite material with ternary shell layer |
| CN114044539A (en) * | 2021-10-30 | 2022-02-15 | 湖南海利锂电科技股份有限公司 | Preparation method of high-cycle power type lithium manganate |
| CN115028201A (en) * | 2022-05-23 | 2022-09-09 | 荆门市格林美新材料有限公司 | Preparation method and application of spherical MnOOH |
| CN115028201B (en) * | 2022-05-23 | 2023-11-21 | 荆门市格林美新材料有限公司 | Spherical MnOOH preparation method and application thereof |
| CN115611317A (en) * | 2022-11-10 | 2023-01-17 | 浙江格派钴业新材料有限公司 | Preparation method of precursor material of high-tap anion-cation doped manganous-manganic oxide |
| CN115611317B (en) * | 2022-11-10 | 2023-11-10 | 浙江格派钴业新材料有限公司 | Preparation method of precursor material with high tap density and cation doped trimanganese tetroxide |
| CN115724468A (en) * | 2022-11-21 | 2023-03-03 | 中钢天源股份有限公司 | Preparation method of pre-doped lithium manganate precursor material and product thereof |
| CN115724468B (en) * | 2022-11-21 | 2024-03-19 | 中钢天源股份有限公司 | Preparation method of pre-doped lithium manganate precursor material and product thereof |
| CN116759561A (en) * | 2023-08-14 | 2023-09-15 | 中冶长天国际工程有限责任公司 | Bulk phase doped and surface coated manganous-manganic oxide material |
| CN116759561B (en) * | 2023-08-14 | 2023-11-14 | 中冶长天国际工程有限责任公司 | Bulk phase doped and surface coated manganous-manganic oxide material |
| CN117105275A (en) * | 2023-10-23 | 2023-11-24 | 湘潭电化科技股份有限公司 | Spherical manganous-manganic oxide and preparation method and application thereof |
| CN117105275B (en) * | 2023-10-23 | 2024-01-12 | 湘潭电化科技股份有限公司 | Spherical manganous-manganic oxide and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107240692A (en) | A kind of spherical lithium manganate doped preparation method | |
| CN105990577B (en) | A kind of anode material for lithium-ion batteries LiNi0.6-xCo0.2Mn0.2AlxO2-yFyAnd preparation method thereof | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN106910887B (en) | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material | |
| CN103078109A (en) | Gradient coated LiNiO2 material and preparation method | |
| CN104241630B (en) | Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof | |
| CN110540254A (en) | Boron-magnesium co-doped gradient nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN102034967A (en) | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery | |
| CN111403729A (en) | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN103022471B (en) | Improve the method for nickelic tertiary cathode material chemical property | |
| CN103441238A (en) | Mg-doped Li-rich anode material and preparation method for same | |
| CN106006762A (en) | Preparation of pedal-layered Ni-Co-Mn ternary material precursor and application of precursor as cathode material for lithium ion cell | |
| CN113809294A (en) | Cobalt-free high-nickel ternary positive electrode material, preparation method and method for preparing battery positive electrode | |
| WO2023109194A1 (en) | Positive electrode material with high peak-intensity ratio, and preparation method therefor and use thereof | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof | |
| CN111682174A (en) | Antimony-coated lithium battery positive electrode material and preparation method and application thereof | |
| CN106602046A (en) | Lithium ion battery silicate cathode material, and preparation and application thereof | |
| CN107768628B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN106784657A (en) | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material | |
| CN109742375B (en) | Surface layer recombined La2Ni0.5Li0.5O4And surface layer doped with La3+NCM ternary positive electrode material | |
| CN113488633B (en) | Titanium magnesium phosphate coated high-nickel ternary or lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN102306764A (en) | Layered LiNiMnCoO composite oxide cathode material and preparation method thereof | |
| CN106571447A (en) | Embedded cladding-type nickel cobalt aluminium lithium material for lithium ion battery and preparation method thereof | |
| CN108321374A (en) | A kind of iron and fluorin-doped composite material and preparation method | |
| CN104241638A (en) | Application of nickel based material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171205 Address after: 545616 the Guangxi Zhuang Autonomous Region Liuzhou Liu Dong New Area Luorong town Applicant after: Guangxi Guiliu Chemical Co.,Ltd. Applicant after: Guangxi Baise de Liu Manganese Industry Co., Ltd. Address before: 545616 the Guangxi Zhuang Autonomous Region Liuzhou Liu Dong New Area Luorong town Applicant before: Guangxi Guiliu Chemical Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20171010 |
|
| WW01 | Invention patent application withdrawn after publication |