CN104051726B - The preparation method of LiMn2O4 - Google Patents
The preparation method of LiMn2O4 Download PDFInfo
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- CN104051726B CN104051726B CN201410298364.2A CN201410298364A CN104051726B CN 104051726 B CN104051726 B CN 104051726B CN 201410298364 A CN201410298364 A CN 201410298364A CN 104051726 B CN104051726 B CN 104051726B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention belongs to the preparation method of LiMn2O4, comprise the steps: one, by lithium salts, manganese salt and doped metallic elements are respectively put in disintegrating apparatus to be pulverized, and is crushed to less than 5 microns；Two, the lithium salts after pulverizing in step one, manganese salt and doped metallic elements press lithium, manganese, Mn+The ratio that mol ratio is 1～1.1: 2X: 2 (1 X) mix；Three, vacuum tank is used to carry out evacuation process material after mixing in step 2；Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s, recovers normal pressure, makes above-mentioned material be pressed into dense state under atmospheric pressure；Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere；The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, is finished product；There is method simple, fast reaction, the advantage that gram volume is high.
Description
Technical field
The invention belongs to cell positive material preparation method technical field, be specifically related to a kind of method simple, quickly
Reaction, the preparation method of the LiMn2O4 that gram volume is high.
Background technology
Along with various portable type electronic products become increasingly popular, battery is as a kind of power-supply device day easy to carry
Benefit receives publicity, and China has become as battery production and consumption big country, the annual waste and old hydrogen nickel produced and cadmium nickel
Environment is caused pollution greatly containing heavy metal nickel, cadmium etc. by battery.In the face of the whole world is more and more tighter to environmental protection
The requirement of lattice, development green energy resource is extremely urgent, the high performance green lithium rechargeable battery that fills, in recent years
To be used widely in various portable type electronic products and communication tool, and by progressively exploitation for electronic
The electrical source of power of automobile.Performance and the cost of lithium ion battery depend greatly on positive electrode, just
The specific capacity of pole material often improves 50%, and the power density of battery can improve 28%, and the specific capacity of negative material is every
Improving 50%, the power density of battery can improve 13% accordingly.The specific volume of lithium ion battery negative material at present
Amount reaches the twice of positive electrode, and positive electrode actual specific capacity is low has become as restriction lithium ion battery development
Bottleneck, therefore study anode material for lithium-ion batteries, for development and improve lithium ion battery have important
Realistic meaning, thus the development of positive electrode becomes crucial.
LiMn2O4, as a kind of novel anode material for lithium-ion batteries, has many advantages, promoter manganese is abundant,
It is cheap, less without heavy metal, environmental pollution, and lithium manganate battery security performance is excellent.But,
Owing to lithium ion battery production cost is higher, limit its large-scale application, be primarily now applied to electronics and produce
Product field, and market scale bigger electric vehicle field application scale the least.Thus reduce into
This has become key, from the point of view of LiMn2O4 angle, it is achieved the fast and efficient production of LiMn2O4 is particularly significant.Improve
Measure is concentrated mainly on reduction production cost and improves product gram volume two aspect.
Summary of the invention
It is an object of the invention to overcome defect of the prior art, and provide a kind of method simple, fast reaction,
The preparation method of the LiMn2O4 that gram volume is high.
The object of the present invention is achieved like this: this preparation method comprises the steps:
One, by lithium salts, manganese salt and doped metallic elements are respectively put in disintegrating apparatus to be pulverized, and is crushed to 5
Below Wei meter；
Two, the lithium salts after pulverizing in step one, manganese salt and doped metallic elements press lithium, manganese, Mn+Mol ratio
It is that the ratio of 1～1.1: 2X: 2 (1-X) mixes, obtains mixed material；Described X in the range of
0.9～1；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09～-0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 750～850 DEG C, at calcining
The time of reason is 8～24 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Lithium salts in described step one is selected from one of lithium carbonate or Lithium hydrate；Manganese salt in described step one
Selected from manganese oxalate, manganese acetate, manganese carbonate, one of manganese dioxide or mangano-manganic oxide；In described step one
Doped metallic elements selected from magnesium, titanium, aluminum, niobium, chromium, one or more in zinc or rare earth element.
The preparation method of a kind of LiMn2O4, comprises the steps:
One, Lithium hydrate, manganese acetate and zinc are respectively put in disintegrating apparatus to be pulverized, and is crushed to 3 microns；
Two, the Lithium hydrate after pulverizing in step one, manganese acetate and zinc press lithium, manganese, Mn+Mol ratio be 1:
The ratio of 1.8: 0.2 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 780 DEG C, calcination processing time
Between be 12 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by lithium carbonate, mangano-manganic oxide is respectively put in disintegrating apparatus and pulverizes, and is crushed to 2 microns；
Two, lithium salts and manganese salt after pulverizing in step one are carried out in the ratio that mol ratio is 1.1: 2 of lithium, manganese
Mixing, obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 835 DEG C, calcination processing time
Between be 22 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh,
It is finished product.
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by Lithium hydrate, manganese dioxide and magnesium are respectively put in disintegrating apparatus to be pulverized, and is crushed to 1 micro-
Rice；
Two, the Lithium hydrate after pulverizing in step one, manganese dioxide and magnesium press lithium, manganese, Mn+Mol ratio be
The ratio of 1.05: 1.9: 0.1 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 850 DEG C, calcination processing time
Between be 9 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Heretofore described material mixing is dry mixed, and dry mixed is without the liquid such as water or ethanol
Dispersant, directly mixes；Disintegrating apparatus jet mill, ball mill, hammer in described step one
One of pulverizer and Raymond mill；The mixing apparatus used by mixing in described step 2 is inclined mixer, crouches
Formula blender, hard one of formula blender, ball mill.The calciner that in described step 5, calcination processing uses
For tunnel cave, tube furnace, clock hood type furnace, rotary furnace, steel belt furnace, vacuum drying oven, sealed or gas circulating type
One of stove.
Synthetic lithium manganate raw materials of the present invention is pressed powder, and in course of reaction, can various elements uniform
Quickly diffusion couple reaction result impact is huge, mainly by refinement feed particles granularity and increasing in building-up process
Add two kinds of approach of exposure level between raw material and solve diffusion problem.Traditional dry production mode is first by various
Raw material is prepared, then co-grinding.Between different raw materials, not only grain graininess differs greatly, and firmly
Degree there is also bigger difference.Different raw materials are put together when grinding, and the less hardness of those granularities is higher
Raw material be difficult to crushed refinement.Between the raw material after being pulverized and mixed, loosely-packed is together, contact area
Little；Or suppress through malleation high pressure, but owing to the raw material after co-grinding is relatively thin, powder body exists more sky
Gap, during high pressure compacting, owing in powder, air is more, compacting contact relatively fruit is the most undesirable.To former in the present invention
Material is pulverized respectively, makes various raw material fully be refined.Then by the raw material mixing after refinement,
And through vacuum compression together, starting material is tight.Thus reach raw materials particles particle size reduction, raw material
Between be in close contact purpose.Thus product synthetic ratio of the present invention is higher, gram volume can reach 125mAh/g,
120mAh/g higher than traditional method.The present invention is dry pulverization process mixing, mixes relative to waterproof pulverization, powder
Broken mixed process does not use ethanol, is not required to after mixing material is dried process, reduces production cost；
There is method simple, fast reaction, the advantage that gram volume is high.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the present invention.
Fig. 2 is the 0.1C charging and discharging curve figure of the present invention.
Detailed description of the invention
The present invention is the preparation method of LiMn2O4, is further described the present invention in conjunction with specific embodiment.
Specific embodiment is as follows:
Embodiment 1
The preparation method of a kind of LiMn2O4, comprises the steps:
One, Lithium hydrate, manganese acetate and zinc are respectively put in disintegrating apparatus to be pulverized, and is crushed to 3 microns；
Two, the Lithium hydrate after pulverizing in step one, manganese acetate and zinc press lithium, manganese, Mn+Mol ratio be 1:
The ratio of 1.8: 0.2 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 780 DEG C, calcination processing time
Between be 12 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 2
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by lithium carbonate, mangano-manganic oxide is respectively put in disintegrating apparatus and pulverizes, and is crushed to 2 microns；
Two, lithium salts and manganese salt after pulverizing in step one are carried out in the ratio that mol ratio is 1.1: 2 of lithium, manganese
Mixing, obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 835 DEG C, calcination processing time
Between be 22 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 3
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by Lithium hydrate, manganese dioxide and magnesium are respectively put in disintegrating apparatus to be pulverized, and is crushed to 1 micro-
Rice；
Two, the Lithium hydrate after pulverizing in step one, manganese dioxide and magnesium press lithium, manganese, Mn+Mol ratio be
The ratio of 1.05: 1.9: 0.1 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 850 DEG C, calcination processing time
Between be 9 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 4
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by Lithium hydrate, manganese oxalate and titanium are respectively put in disintegrating apparatus to be pulverized, and is crushed to 4 microns；
Two, the Lithium hydrate after pulverizing in step one, manganese oxalate and titanium press lithium, manganese, Mn+Mol ratio be 1.1:
The ratio of 1.9: 0.1 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 785 DEG C, calcination processing time
Between be 22 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 5
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by lithium carbonate, manganese carbonate and rare earth element are respectively put in disintegrating apparatus to be pulverized, and is crushed to 5
Micron；
Two, the lithium carbonate after pulverizing in step one, manganese carbonate and rare earth element press lithium, manganese, Mn+Mol ratio
Be 1: 1.82: 0.18 ratio mix, obtain mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 830 DEG C, calcination processing time
Between be 12 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 6
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by Lithium hydrate, manganese dioxide and aluminum are respectively put in disintegrating apparatus to be pulverized, and is crushed to 5 micro-
Below meter；
Two, the Lithium hydrate after pulverizing in step one, manganese dioxide and aluminum press lithium, manganese, Mn+Mol ratio be
The ratio of 1.1: 1.84: 0.16 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 820 DEG C, calcination processing time
Between be 10 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 7
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by lithium carbonate, mangano-manganic oxide and chromium are respectively put in disintegrating apparatus to be pulverized, and is crushed to 3 micro-
Rice；
Two, the lithium carbonate after pulverizing in step one, mangano-manganic oxide and chromium press lithium, manganese, Mn+Mol ratio be 1:
The ratio of 1.94: 0.06 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 800 DEG C, calcination processing time
Between be 16 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 8
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by lithium carbonate, manganese acetate and niobium are respectively put in disintegrating apparatus to be pulverized, and is crushed to 2 microns；
Two, the lithium salts after pulverizing in step one, manganese salt and doped metallic elements press lithium, manganese, Mn+Mol ratio
Be 1.1: 1.92: 0.08 ratio mix, obtain mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 750 DEG C, calcination processing time
Between be 24 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Embodiment 9
The preparation method of a kind of LiMn2O4, comprises the steps:
One, by lithium carbonate, manganese oxalate and doped metallic elements are respectively put in disintegrating apparatus to be pulverized, and pulverizes
To 800 nanometers；Described doped metallic elements includes aluminum, niobium, chromium, zinc and rare earth element；
Two, the lithium carbonate after pulverizing in step one, manganese oxalate and doped metallic elements press lithium, manganese, Mn+Rub
You mix than the ratio being 1.1: 1.88: 0.12, obtain mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 810 DEG C, calcination processing time
Between be 15 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
Above example only in order to explain technical solution of the present invention, is not intended to limit；Although with reference to aforementioned enforcement
The present invention has been described in detail by example, it will be understood by those within the art that, it is the most permissible
Technical scheme described in aforementioned each example is modified, or wherein portion of techniques feature is equal to
Replace；And these amendments or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention skill
The spirit and scope of art scheme.
Experimental example, the LiMn2O4 obtained by the preparation method of the present invention as described in Example 8, as it is shown in figure 1,
It is the XRD figure of the present invention by Fig. 1, it is known that the present invention is the pure LiMn2O4 product without dephasign；Such as Fig. 2
Shown in, by the 0.1C charging and discharging curve figure of Fig. 2 present invention, it is known that the gram volume of product of the present invention reaches
125mAh/g。
Claims (5)
1. the preparation method of a LiMn2O4, it is characterised in that: this preparation method comprises the steps:
One, by lithium salts, manganese source and doped metallic elements are respectively put in disintegrating apparatus to be pulverized, and is crushed to 5
Below Wei meter；Manganese source in described step one be selected from manganese oxalate, manganese acetate, manganese carbonate, manganese dioxide or
One of mangano-manganic oxide；
Two, the lithium salts after pulverizing in step one, manganese source and doped metallic elements press lithium, manganese, Mn+Mol ratio
It is that the ratio of 1～1.1: 2X: 2 (1-X) mixes, obtains mixed material；Described X in the range of
0.9～1；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09～-0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 750～850 DEG C, at calcining
The time of reason is 8～24 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
The preparation method of LiMn2O4 the most according to claim 1, it is characterised in that: in described step one
Lithium salts selected from one of lithium carbonate or Lithium hydrate；Doped metallic elements in described step one selected from magnesium,
One or more in titanium, aluminum, niobium, chromium, zinc or rare earth element.
The preparation method of LiMn2O4 the most according to claim 1, it is characterised in that: this preparation method includes
Following steps:
One, Lithium hydrate, manganese acetate and zinc are respectively put in disintegrating apparatus to be pulverized, and is crushed to 3 microns；
Two, the Lithium hydrate after pulverizing in step one, manganese acetate and zinc press lithium, manganese, Mn+Mol ratio be 1:
The ratio of 1.8: 0.2 mixes, and obtains mixed material；
Three, using vacuum tank to carry out evacuation process material after the mixing described in step 2, vacuum is one
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 780 DEG C, calcination processing time
Between be 12 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh, i.e.
For finished product.
The preparation method of LiMn2O4 the most according to claim 1, it is characterised in that: this preparation method includes
Following steps:
One, by lithium carbonate, mangano-manganic oxide is respectively put in disintegrating apparatus and pulverizes, and is crushed to 2 microns；
Two, lithium salts and manganese source after pulverizing in step one are carried out in the ratio that mol ratio is 1.1: 2 of lithium, manganese
Mixing, obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.09MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 835 DEG C, calcination processing time
Between be 22 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh,
It is finished product.
The preparation method of LiMn2O4 the most according to claim 1, it is characterised in that: this preparation method includes
Following steps:
One, by Lithium hydrate, manganese dioxide and magnesium are respectively put in disintegrating apparatus to be pulverized, and is crushed to 1 micro-
Rice；
Two, the Lithium hydrate after pulverizing in step one, manganese dioxide and magnesium press lithium, manganese, Mn+Mol ratio be
The ratio of 1.05: 1.9: 0.1 mixes, and obtains mixed material；
Three, vacuum tank is used to carry out evacuation process material after the mixing described in step 2, vacuum is-
0.1MPa；
Four, after the mixing after carrying out evacuation process described in step 3, material rapidly removes vacuum in 10s,
Recover normal pressure, make above-mentioned material be pressed into dense state under atmospheric pressure；
Five, the material being pressed into dense state in step 4 is carried out calcination processing in air atmosphere, calcining
Naturally cooling to room temperature after process, temperature range during described calcination processing is 850 DEG C, calcination processing time
Between be 9 hours；
The crushing material that six, material after calcination processing described in step 5 is cooled to room temperature is 250 mesh,
It is finished product.
Priority Applications (1)
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