CN105914351A - Preparation method of spinel type lithium manganate or lithium nickel manganese oxide - Google Patents
Preparation method of spinel type lithium manganate or lithium nickel manganese oxide Download PDFInfo
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- CN105914351A CN105914351A CN201610232591.4A CN201610232591A CN105914351A CN 105914351 A CN105914351 A CN 105914351A CN 201610232591 A CN201610232591 A CN 201610232591A CN 105914351 A CN105914351 A CN 105914351A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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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- 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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- 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
- H01M4/52—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the invention discloses a preparation method of spinel type lithium manganate or lithium nickel manganese oxide. The method includes: mixing a lithium source, a substance M and a base material to obtain a precursor; and conducting calcination treatment on the precursor to obtain a target product. The substance M includes a manganese source, or the substance M includes a manganese source and a nickel source, under the circumstance that the substance M includes the manganese source, the target product is spinel type lithium manganate, and under the circumstance that the substance M includes the manganese source and the nickel source, the target product is spinel type lithium nickel manganese oxide. The base material is plant fiber with a hollow structure, preferably at least one of wood pulp fiber and cotton pulp, and the weight of the base material is not less than 1% of the total weight of the lithium source and the substance M. The scheme ensures that in a calcination process, the precursor at different positions can contact oxygen more uniformly, so that the spinel type lithium manganate or lithium nickel manganese oxide has good structural consistency.
Description
Technical field
The present invention relates to field of lithium ion battery anode, particularly to a kind of lithium manganate having spinel structure or the preparation method of nickel ion doped.
Background technology
Lithium manganate having spinel structure and spinel-type nickel ion doped are the most relatively conventional commercial lithium cell positive materials.Wherein, lithium manganate having spinel structure has spinel structure, and the chemical formula of the LiMn2O4 of stoichiometric proportion is LiMn2O4, belong to cubic system, there is Fd-3m (227) symmetry.8 tetrahedral sites (8a) that its elementary cell by 32 oxygen and is made up of them and 16 octahedral sites (16d), oxygen atom uses cubic close to pile up (CCP) form, lithium ion is in tetrahedral 8a position, manganese ion is in octahedral 16d position, and 16d position is respectively by Mn3+And Mn4+Occupying, the mol ratio between them is 1:1, and octahedral 16c position is empty.After the Mn of 1/4 is replaced by Ni in lithium manganate having spinel structure, can obtain nickel ion doped, its structure is still spinel structure, and chemical formula is LiNi0.5Mn1.5O4, manganese valence is all upgraded to 4 valencys.
For lithium manganate having spinel structure, prepared by industrial mainly employing solid-phase synthesis, lithium source (hydroxide of such as lithium, carbonate or nitrate etc.) and manganese source (oxide of manganese, hydroxide or carbonate etc.) mixed by the method by a certain percentage, grind and prepare presoma after, presoma is placed in saggar at high temperature such as 700-900 DEG C calcining a few hours, in the presence of oxygen, presoma can change into lithium manganate having spinel structure.This solid-phase synthesis flow process is simple, easily operates, and is suitable for industrial application.But in calcination process, be positioned at the presoma of diverse location in saggar and contact with oxygen and differ greatly, such as, the presoma on saggar surface readily accesses oxygen, and the presoma within saggar is difficult to touch oxygen；So surface readily accesses the lithium manganate having spinel structure Mn in composition that the presoma of oxygen generated and is easily oxidised as+trivalent and+4 valencys, and in structure, manganese ion is prone to be present in the position of 16d；And inside is less easily accessible to the presoma of oxygen, it is difficult to due to hypoxgia make reaction carry out completely, the lithium manganate having spinel structure generated structurally is prone to fault of construction occur, such as in the position of 16d, lithium ion is also easy to enter and mix existence with manganese ion, ultimately result in calcining lithium manganate having spinel structure crystal structure concordance out bad, and use this lithium manganate having spinel structure as the lithium battery of positive electrode, its electric property will show the problems such as capacity is low, cyclical stability is poor.
After replacing manganese source by a certain amount of nickel source, use the method can synthesize spinel-type nickel ion doped, it is clear that the method, when preparing nickel ion doped, there is also identical problem.The particularly so-called 5V positive electrode LiNi of synthesis0.5Mn1.5O4The when of spinel-type nickel ion doped, owing to manganese valence is 4+Valency, and oxidizing atmosphere is required higher.
Summary of the invention
The embodiment of the invention discloses the preparation method of a kind of lithium manganate having spinel structure or nickel ion doped, the problem that during for solving to use solid-phase synthesis to prepare lithium manganate having spinel structure or nickel ion doped, crystal structure concordance is bad.Technical scheme is as follows:
A kind of lithium manganate having spinel structure or the preparation method of nickel ion doped, including:
Lithium source, material M and base material are mixed, it is thus achieved that presoma；
By presoma calcination processing, obtain target product；
Wherein, described material M includes manganese source, or described material M includes manganese source and nickel source；And in the case of described material M includes manganese source, described target product is lithium manganate having spinel structure；In the case of described material M includes manganese source and nickel source, described target product is spinel-type nickel ion doped；
Described base material is the Plant fiber with hollow structure, it is preferably: at least one in wood pulp cellulose and Cotton Pulp, and the weight of base material is not less than lithium source and the 1% of material M gross weight, preferably 1%-20%, more preferably 1-10%, most preferably 1%-6%.
In the preferred embodiment of the present invention, described by the mixing of lithium source, material M and base material, it is thus achieved that presoma, including:
After lithium source, material M and base material are mixed, grind uniformly, it is thus achieved that presoma.
In the preferred embodiment of the present invention, described by the mixing of lithium source, material M and base material, it is thus achieved that presoma, including:
Lithium source, material M and base material are added in water, after mix homogeneously, dried, it is thus achieved that presoma.
In the preferred embodiment of the present invention, in the case of described material M includes manganese source, the mol ratio in described lithium source and manganese source is Li:Mn=1:(1.7-2), preferably Li:Mn=1:2.
In the preferred embodiment of the present invention, in the case of described material M includes manganese source and nickel source, the mol ratio in described lithium source, nickel source and manganese source is Li:Ni:Mn=1:(0.4-0.5): (1.2-1.5), preferably Li:Ni:Mn=1:0.5:1.5.
In the preferred embodiment of the present invention, described manganese source is selected from least one in manganese acetate, formic acid manganese, manganese nitrate and manganese carbonate.
In the preferred embodiment of the present invention, described lithium source is selected from least one in lithium acetate, lithium formate, lithium nitrate, lithium ethoxide and lithium carbonate.
In the preferred embodiment of the present invention, described nickel source is selected from least one in nickel acetate, nickel nitrate, nickel formate and Nickel tetracarbonyl..
In the preferred embodiment of the present invention, adding dispersant in water, the addition of described dispersant is lithium source and the 0.1%-1% of material M gross weight.
In the preferred embodiment of the present invention, described dispersant is selected from least one in methanol and ethanol.
From above-mentioned scheme, the present invention is when preparing lithium manganate having spinel structure or nickel ion doped, there is the Plant fiber of hollow structure as base material, and be mixed with being formed uniformly precursor by lithium source, manganese source or lithium source, manganese source and nickel source, in calcination process, the air in fiber lumen can be that precursor changes into lithium manganate having spinel structure offer oxygen.Ensureing in calcination process, the precursor of diverse location evenly can touch oxygen, so that lithium manganate having spinel structure or nickel ion doped structural integrity are good.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in describing below is only some embodiments of the present invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
When Fig. 1 a is for using embodiment 1 to prepare lithium manganate having spinel structure, the LiMn2O4 XRD figure of upper surface in saggar；
When Fig. 1 b is for using embodiment 1 to prepare lithium manganate having spinel structure, the LiMn2O4 XRD figure of mid portion in saggar；
When Fig. 1 c is for using embodiment 1 to prepare lithium manganate having spinel structure, the LiMn2O4 XRD figure of saggar inner bottom part；
When Fig. 2 a is for using comparative example 1 to prepare lithium manganate having spinel structure, the LiMn2O4 XRD figure of upper surface in saggar；
When Fig. 2 b is for using comparative example 1 to prepare lithium manganate having spinel structure, the LiMn2O4 XRD figure of mid portion in saggar；
When Fig. 2 c is for using comparative example 1 to prepare lithium manganate having spinel structure, the LiMn2O4 XRD figure of saggar inner bottom part；
Fig. 3 a is to use embodiment 1 to prepare lithium manganate having spinel structure as charge-discharge performance test result during anode；
Fig. 3 b is to use comparative example 1 to prepare lithium manganate having spinel structure as charge-discharge performance test result during anode；
The position view of sampling when Fig. 4 is to test the LiMn2O4 prepared by embodiment 1 and comparative example 1.
Detailed description of the invention
The invention provides the preparation method of a kind of lithium manganate having spinel structure or nickel ion doped, first lithium source, material M and base material are mixed, it is thus achieved that presoma；Wherein, when the method provided by the present invention prepares lithium manganate having spinel structure, described material M includes manganese source, say, that lithium source, manganese source and base material are mixed, it is thus achieved that presoma；When the method provided by the present invention prepares spinel-type nickel ion doped, described material M includes manganese source and nickel source, say, that lithium source, manganese source, nickel source and base material are mixed, it is thus achieved that presoma；
Described base material is the Plant fiber with hollow structure, base material is preferably: at least one in wood pulp cellulose (including softwood pulp fiber and hardwood pulp fiber) and Cotton Pulp, the weight of base material is not less than lithium source and the 1% of material M gross weight, it is preferably 1%-20%, more preferably 1-10%, most preferably 1%-6%.
There is the Plant fiber of hollow structure, its internal hollow structure (cavity) can store air, and the present invention utilizes its this feature to realize the goal of the invention of the present invention just, i.e. in calcination process, the air in fiber lumen can be that precursor changes into lithium manganate having spinel structure offer oxygen.Ensureing in calcination process, the precursor of diverse location evenly can touch oxygen, so that lithium manganate having spinel structure or nickel ion doped structural integrity are good.All can be obtained by commercially available approach it should be noted that have the Plant fiber of hollow structure, such as wood pulp cellulose and Cotton Pulp.
The present invention is in specific implementation process, it is preferred to use lithium source, material M and base material are mixed by two ways below, it is thus achieved that presoma.
First kind of way, after lithium source, material M and base material being mixed, grinds uniformly, it is thus achieved that presoma.Concrete, ball mill ball milling etc. can be used, grinding technics is routine techniques, and the present invention is not defined at this.In general, those skilled in the art easily determine out the whether uniform of grinding, and therefore, the present invention is without being defined milling time, such as, generally grind 10-15h (hour).
Lithium source, material M and base material are added in water by the second way, after mix homogeneously, and dried, it is thus achieved that presoma.In this kind of mode, first lithium source, material M can be dissolved in the water, then in water, add base material and stir, obtain soliquid, first base material can also be dispersed in water, the most again lithium source, material M are added to the water, obtain soliquid；Then by this soliquid dried, until without the water of flowing, such as can be dried 14 hours at 110 DEG C.Owing to base material has certain thickening power, therefore, even if manganese source, lithium source and nickel source are water insoluble, under the effect of base material, it is also possible to be uniformly dispersed in water.
In the manner, in order to accelerate the mix homogeneously of various material, it is also possible to add a small amount of dispersant, preferably methanol and ethanol in water.The addition of dispersant can be lithium source and the 0.1%-1% of material M gross weight.
For the consumption of aqueous solvent, there is no special requirement, it can only fully dissolve or disperse lithium source, material M and base material.Such as, the addition of water can be at about 1:1mL/g with the ratio of lithium source and material M gross weight.
In above-mentioned each embodiment, when preparing lithium manganate having spinel structure, namely in the case of described material M includes manganese source, the mol ratio in described lithium source and manganese source is Li:Mn=1:(1.7-2), preferably Li:Mn=1:2.
When preparing spinel-type nickel ion doped, namely in the case of described material M includes manganese source and nickel source, the mol ratio in described lithium source, nickel source and manganese source is Li:Ni:Mn=1:(0.4-0.5): (1.2-1.5), preferably Li:Ni:Mn=1:0.5:1.5.
Manganese source, lithium source and nickel source employed in the present invention, not particular/special requirement, general this area for prepare lithium manganate having spinel structure or the manganese source of nickel ion doped, lithium source and nickel source may be incorporated for realizing the present invention, preferably, manganese source can be selected from least one in manganese acetate, formic acid manganese, manganese nitrate and manganese carbonate；Lithium source can be selected from least one in lithium acetate, lithium formate, lithium nitrate, lithium ethoxide and lithium carbonate；Nickel source can be selected from least one in nickel acetate, nickel nitrate, nickel formate and Nickel tetracarbonyl..
After obtaining presoma, it is possible to presoma is calcined, makes presoma be converted into target product, i.e. lithium manganate having spinel structure or spinel-type nickel ion doped.This step process can use existing solid-phase synthesis to realize, and the present invention the most specifically limits at this, usually, calcines 2-6 hour at 700-900 DEG C.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment
1
Ratio according to Li:Mn=1:1.8, weigh 11.1g (0.15mol) lithium carbonate and 62g (0.54mol) manganese carbonate, it is dissolved in 70mL water, 4.4g Cotton Pulp (the CP1000u type Cotton Pulp that Shandong highly dense chemical fibre Group Co., Ltd produces) is weighed according to the 6% of lithium carbonate and manganese carbonate gross weight, it is added to the water, stir, obtain soliquid, then soliquid is dried 14 hours at 110 DEG C, obtain presoma, again presoma is positioned in saggar, 800 DEG C of high-temperature calcinations 4 hours, obtains lithium manganate having spinel structure.
Embodiment
2
Ratio according to Li:Mn=1:2, weigh 11.1g (0.15mol) lithium carbonate and 69g (0.6mol) manganese carbonate, 2.4g Cotton Pulp is weighed according to the 3% of lithium carbonate and manganese carbonate gross weight, by three ball mill ball milling 10 hours, again 800 DEG C of high-temperature calcinations 4 hours, obtain lithium manganate having spinel structure.
Embodiment
3
Ratio according to Li:Ni:Mn=1:0.5:1.5, weigh 6.9g (0.1mol) lithium nitrate, 14.5g (0.05mol) nickel nitrate (Nickelous nitrate hexahydrate), 17.2g (0.15mol) manganese carbonate, it is dissolved in 40mL water, according to lithium nitrate, the 1% of nickel nitrate and manganese carbonate and gross weight weighs 0.39g wood pulp cellulose (the Russian Yi Limu company that Sinotrans accumulating company limited provides produces Lot145444-crow pin slurry), it is added to the water, stir, obtain soliquid, then soliquid is dried 14 hours at 110 DEG C, again 800 DEG C of high-temperature calcinations 4 hours, obtain spinel-type nickel ion doped.
Embodiment
4
Ratio according to Li:Ni:Mn=1:0.4:1.2, weigh 6.9g (0.1mol) lithium nitrate and 11.6g (0.04mol) nickel nitrate, 13.8g (0.12mol) manganese carbonate, 3.3g wood pulp cellulose is weighed according to the 10% of lithium nitrate, nickel nitrate and manganese carbonate and gross weight, by three at ball mill ball milling 10h, again 800 DEG C of high-temperature calcinations 4 hours, obtain spinel-type nickel ion doped.
Embodiment
5
Embodiment 5 is with the difference of embodiment 3, weighs 7.7g wood pulp cellulose according to the 20% of lithium nitrate, nickel nitrate and manganese carbonate and gross weight, and adds ethanol 0.02g as dispersant, identical both other.
Comparative example
1
Use starch to replace Cotton Pulp, first starch is dissolved in 70mL water, heating so that it is become the aqueous solution of thickness, then add lithium carbonate and manganese carbonate；Stir, obtain soliquid, then soliquid is dried 14 hours at 110 DEG C, it is thus achieved that presoma, then presoma is positioned in saggar, 800 DEG C of high-temperature calcinations 4 hours, obtain lithium manganate having spinel structure.Amount used by each material is the most same as in Example 1.
Characterize and test
XRD tests
After embodiment 1 has been calcined and has been cooled to room temperature, as shown in Figure 4, the lithium manganate having spinel structure taking upper surface 01 in saggar 04, mid portion 02 and bottom 03 respectively carries out XRD test, respectively as shown in Fig. 1 a, Fig. 1 b and Fig. 1 c.
Same, after comparative example 1 has been calcined and has been cooled to room temperature, the lithium manganate having spinel structure taking upper surface 01 in saggar 04, mid portion 02 and bottom 03 respectively carries out XRD test, respectively as shown in Fig. 2 a, Fig. 2 b and Fig. 2 c.
From Fig. 1 a, Fig. 1 b and Fig. 1 c it can be seen that in saggar, the lithium manganate having spinel structure diffraction peak-to-peak type of upper surface, mid portion and bottom is consistent, and being pure material does not has impurity mutually.Do not have to be affected by how many with air contact.
From Fig. 2 a, Fig. 2 b and Fig. 2 c it can be seen that in saggar the diffraction maximum of the lithium manganate having spinel structure of upper surface, mid portion and bottom substantially affected by how many with air contact.Upper surface more with air contact is pure phase, and middle and bottom all occurs producing the manganese sesquioxide managnic oxide that degree of oxidation is inadequate because of anoxia, and bottom is even more serious than mid portion, and its manganese sesquioxide managnic oxide main peak substantially increases, and i.e. creates more manganese sesquioxide managnic oxide impurity.
Visible, use technical scheme, all can obtain the lithium manganate having spinel structure that structural integrity is good for the diverse location in saggar, it is to be understood that for spinel-type nickel ion doped, equally obtain the result that structural integrity is good.
Charge-discharge performance is tested
The LiMn2O4 that embodiment 1 and comparative example 1 are obtained, the purest phase spinel lithium manganate and have the spinel lithium manganate of impurity, the method with same: take the lithium manganate having spinel structure of three diverse locations of upper, middle and lower in saggar, after mixing, be fabricated to positive plate respectively.It is respectively less than in the glove box of 0.1ppm at full high-purity argon gas, water and oxygen concentration, with metal lithium sheet as negative pole, according to negative electrode casing, lithium sheet, barrier film, electrolyte, positive plate, steel disc, shell fragment, the sequence of anode cover, is assembled into 2032 button cells.After placing 12h, under constant current mode, it is 4.3V that the charging of battery limits voltage, and final discharging voltage is 3V.Charging current is that 40mA/g carries out charge-discharge performance test.As shown in Figure 3 a, the test result of comparative example 1 is as shown in Figure 3 b for the test result of embodiment 1.
From Fig. 3 a it can be seen that the spinel lithium manganate of pure phase: the specific capacity of charging and discharging, all at about 110mAh/g.Charge and discharge cycles 21 is subnormal and does not has relaxation phenomenon, if the time allows to can also continue to carry out charge and discharge cycles.
From Fig. 3 b it can be seen that there is the spinel lithium manganate of impurity: charging and discharging capacity only has about 60mAh/g, and occurs that charging cannot be full of for 13 times in circulation, it is impossible to be further continued for carrying out charge and discharge cycles.
Visible, the lithium manganate having spinel structure prepared using technical scheme, as the lithium battery of positive electrode, its electric property will show the advantages such as capacity height, good cycling stability.Based on identical principle, spinel-type nickel ion doped prepared by technical scheme, as the lithium battery of positive electrode, its electric property will show the advantages such as capacity height, good cycling stability equally.
Above the preparation method of a kind of lithium manganate having spinel structure provided by the present invention or nickel ion doped is described in detail.Principle and the embodiment of the present invention are set forth by specific embodiment used herein, and the explanation of above example is only intended to help to understand method and the central idea thereof of the present invention.It should be pointed out that, for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement and modification, these improve and modify the protection also falling into the claims in the present invention.
All any modification, equivalent substitution and improvement etc. made within the spirit and principles in the present invention, are all contained in protection scope of the present invention.
Claims (10)
1. a lithium manganate having spinel structure or the preparation method of nickel ion doped, it is characterised in that including:
Lithium source, material M and base material are mixed, it is thus achieved that presoma；
By presoma calcination processing, obtain target product；
Wherein, described material M includes manganese source, or described material M includes manganese source and nickel source；And at described material
In the case of M includes manganese source, described target product is lithium manganate having spinel structure；Manganese source is included at described material M
In the case of nickel source, described target product is spinel-type nickel ion doped；
Described base material is the Plant fiber with hollow structure, is preferably: in wood pulp cellulose and Cotton Pulp
At least one, and the weight of base material is not less than lithium source and the 1% of material M gross weight, is preferably
1%-20%, more preferably 1-10%, most preferably 1%-6%.
2. the method for claim 1, it is characterised in that described by lithium source, material M and base material
Mixing, it is thus achieved that presoma, including:
After lithium source, material M and base material are mixed, grind uniformly, it is thus achieved that presoma.
3. the method for claim 1, it is characterised in that described by lithium source, material M and base material
Mixing, it is thus achieved that presoma, including:
Lithium source, material M and base material are added in water, after mix homogeneously, dried, it is thus achieved that presoma.
4. the method as according to any one of claim 1-3, it is characterised in that include manganese at described material M
In the case of source, the mol ratio in described lithium source and manganese source is Li:Mn=1:(1.7-2), preferably Li:Mn=1:2.
5. the method as according to any one of claim 1-3, it is characterised in that include manganese at described material M
In the case of source and nickel source, the mol ratio in described lithium source, nickel source and manganese source is Li:Ni:
Mn=1:(0.4-0.5): (1.2-1.5), preferably Li:Ni:Mn=1:0.5:1.5.
6. the method as according to any one of claim 1-3, it is characterised in that described manganese source is selected from acetic acid
At least one in manganese, formic acid manganese, manganese nitrate and manganese carbonate.
7. the method as according to any one of claim 1-3, it is characterised in that described lithium source is selected from acetic acid
At least one in lithium, lithium formate, lithium nitrate, lithium ethoxide and lithium carbonate.
8. the method as according to any one of claim 1-3, it is characterised in that described nickel source is selected from acetic acid
At least one in nickel, nickel nitrate, nickel formate and Nickel tetracarbonyl..
9. method as claimed in claim 3, it is characterised in that add dispersant, described dispersion in water
The addition of agent is lithium source and the 0.1%-1% of material M gross weight.
10. method as claimed in claim 9, it is characterised in that described dispersant is selected from methanol and ethanol
In at least one.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450284A (en) * | 2016-11-25 | 2017-02-22 | 桂林理工大学 | Method for preparing hollow-microsphere lithium manganate positive electrode material with higher electrochemical properties |
| CN106745332A (en) * | 2016-11-24 | 2017-05-31 | 云南民族大学 | Combustion method quickly prepares nanometer spinel type nickel ion doped material |
| CN107317024A (en) * | 2017-07-28 | 2017-11-03 | 长安大学 | Lithium-rich manganese-based layered lithium ion battery positive electrode of vinasse auxiliary synthesis and preparation method thereof |
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