CN105161711A - Lithium manganate cathode material, preparation method and use - Google Patents
Lithium manganate cathode material, preparation method and use Download PDFInfo
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- CN105161711A CN105161711A CN201510567812.9A CN201510567812A CN105161711A CN 105161711 A CN105161711 A CN 105161711A CN 201510567812 A CN201510567812 A CN 201510567812A CN 105161711 A CN105161711 A CN 105161711A
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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
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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 invention relates to a preparation method of a lithium manganate cathode material. The preparation method comprises the following steps: (1), mixing manganese source, lithium source and carbon source materials to obtain a precursor; and (2), sintering the precursor obtained in the step (1) in air, and cooling to obtain the lithium manganate cathode material. According to the invention, a carbon material is added into lithium manganate and then sintered, such that the cathode material of a lithium ion battery is obtained; the specific capacity, the rate capability and the cycle performance of the cathode material are excellent; furthermore, the lithium manganate cathode material is high in purity and regular in particle, such that requirements of the lithium ion battery in practical application can be satisfied; and the preparation method of the lithium manganate cathode material of the lithium ion battery provided by the invention is low in cost, simple in step, low in energy consumption and easy to realize large-scale industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of manganate cathode material for lithium, Preparation method and use, be specifically related to the direct mixed-sintering method of a kind of carbon and slaine or oxide and prepare the synthetic method of LiMn2O4, product and purposes.
Background technology
Along with the progress of science and technology and the development of the mankind, the demand of people to the energy is increasing, but present fossil energy reserves are fewer and feweri, and the use of the traditional energy such as fossil energy also constitutes great threat to environment.From eighties of last century eighties, lithium ion battery rises gradually, and has ruled the energy supply of many high-tech mobile devices such as computer, mobile phone.This kind of lithium ion battery is mainly with LiCoO
2/ C is as positive and negative electrode.The range of application of current lithium ion battery is more extensive, and particularly to the development in electric automobile, large-scale energy storage device direction, this gives lithium ion battery, and particularly positive electrode is wherein had higher requirement.
But due to LiCoO
2some defects of material self, impel large quantities of researchers and technical staff to be devoted to seek new positive electrode.The alternative LiCoO of main flow on market
2lithium electricity positive electrode have, the LiFePO of olivine-type
4, layer structure oxide LiMo
2the LiMn of (M represents Co, Ni, Al, Mn mixing), spinel-type
2o
4(LiMn2O4) etc.Wherein, the LiMn of spinel structure
2o
4, because it has three-dimensional lithium ion body phase transmission channel (guaranteeing that it may have high high rate performance), environmental friendliness and nontoxic, the advantages such as abundant raw material make it have great application prospect.
LiMn2O4 has commercially occupied very large proportion as a kind of positive electrode, and industrially large-scale production.As everyone knows, there is close contacting in the performance of material and the synthetic method of material.And the two large subject matters that LiMn2O4 faces as lithium electricity positive electrode are: cyclical stability is poor, high rate performance is poor.So improving LiMn2O4 high rate performance, cycle performance by the synthetic method of seeking new LiMn2O4 and having great importance in reducing costs etc.
Prior art large-scale production LiMn2O4, the method adopted is generally solid sintering technology.The advantage of this method is that technique is simple, advantage of lower cost.But industrially adopt LiMn2O4 produced in this way, its cycle performance and high rate performance can't meet the requirement of market to high-performance positive electrode, make its application commercially limited, so manganate cathode material for lithium price is in the market general lower.
The method of current synthetic lithium manganate also comprises the methods such as sol-gal process, hydro thermal method, combustion method.Adopt the LiMn2O4 synthesized by these methods, its performance is relatively better.But again because these methods exist complex process, high in cost of production problem, make these methods be unsuitable for industrial mass production.So, be badly in need of mousing out that a kind of production cost is low, properties of product are high, be easy to the method for large-scale production.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the preparation method providing a kind of manganate cathode material for lithium, and described method comprises the steps:
(1) mix manganese source, lithium source and carbon source material, obtain presoma;
(2) presoma of step (1) is sintered in atmosphere, after cooling, obtain manganate cathode material for lithium.
The present invention adopts the raw materials of manganate cathode material for lithium and the direct mixed sintering of carbon, successfully synthesizes the LiMn2O4 of high rate capability, high cyclicity and height ratio capacity.
In the preparation process of manganate cathode material for lithium provided by the invention, carbon source material play dispersant, can the effect of ablation template: carbon is oxidation heat liberation at high temperature, make synthesized manganate cathode material for lithium size more homogeneous, shape is more regular, and effectively prevent particle and too reunite; In addition, carbon at high temperature oxidation heat liberation that raw material are heated is more even, and there is high crystallinity, and carbon have can be ablative, through sintering in atmosphere, be oxidized by oxygen as CO
2and remove; Secondly, the synthesis of carbon to LiMn2O4 has facilitation, and high rate performance and the cycle performance of the lithium manganate material obtained improve all greatly.
In presoma of the present invention, the mol ratio of manganese element and elemental lithium is 2:1 ~ 1.2, such as 2:1.05,2:1.1,2:1.15 etc.
In presoma of the present invention, the mol ratio of manganese element and carbon is 0.025 ~ 0.5:1, such as 0.03:1,0.034:1,0.045:1,0.05:1,0.063:1,0.08:1,0.12:1,0.15:1,0.2:1,0.3:1,0.4:1,0.48:1 etc., preferred 0.14:1.
Step of the present invention is sintered to described in (2): first carry out once sintered at 150 ~ 450 DEG C, carry out double sintering at being then warmed up to 550 ~ 850 DEG C.
Described once sintered temperature is typical but non-limiting can be 170 DEG C, 190 DEG C, 220 DEG C, 260 DEG C, 300 DEG C, 360 DEG C, 400 DEG C, 420 DEG C etc.; The temperature of described double sintering is typical but non-limiting can be 570 DEG C, 590 DEG C, 620 DEG C, 660 DEG C, 700 DEG C, 760 DEG C, 800 DEG C, 820 DEG C etc.
Preferably, step (2) the described once sintered time is 1 ~ 10h, such as 2h, 3h, 4h, 5h, 6h, 8h, 9h etc.
Preferably, step (2) the described double sintering time at more than 1h, such as 2h, 7h, 14h, 25h, 36h etc., preferably 1 ~ 48h;
Preferably, step (2) described sintering carries out in Muffle furnace.
Step of the present invention is sintered to described in (2): first at 350 DEG C, carry out once sintered 4h, carry out double sintering 8h at being then warmed up to 700 DEG C.
Carbon source material of the present invention is selected from the combination of any a kind or at least 2 kinds in carbon black, graphite, carbon nano-tube, active carbon; The combination of the typical but non-limiting carbon source material of described combination comprises the combination of carbon black and graphite, the combination of carbon nano-tube and active carbon, the combination etc. of carbon black, graphite and active carbon.
Preferably, described carbon black is conductive carbon black, preferably includes the combination of any a kind or at least 2 kinds in acetylene black, ECP600JD, superpli, KS-6; The combination of the typical but non-limiting carbon black of described combination comprises the combination of acetylene black and superpli, the combination of ECP600JD and KS-6, the combination etc. of acetylene black, ECP600JD and KS-6.
Further preferably, described carbon source material is graphite and/or acetylene black.
Manganese source of the present invention is the combination of any a kind or at least 2 kinds in manganous bromide, manganese carbonate, manganese chloride, manganese oxide, manganese nitrate, manganese oxalate, manganese sulfate, manganese acetate, preferred manganese nitrate and/or manganese acetate.
The combination in the typical but non-limiting manganese source of described combination comprises the combination of manganese oxide and manganese oxalate, the combination of manganese carbonate, manganese chloride and manganous bromide, the combination of manganese carbonate and manganese acetate, the combination etc. of manganese chloride and manganese sulfate.
Preferably, described lithium source is the combination of any a kind or at least 2 kinds in lithium carbonate, lithium hydroxide, lithia, lithium oxalate, lithium acetate, lithium nitrate, preferred lithium nitrate and/or lithium acetate; The combination in the typical but non-limiting lithium source of described combination comprises the combination of lithium carbonate and lithia, the combination of lithium oxalate, lithium acetate and lithium carbonate, the combination of lithium oxalate, lithium acetate and lithium hydroxide, the combination etc. of lithium nitrate and lithia.
A kind of embodiment of step of the present invention (1) described mixing manganese source, lithium source and carbon source material is: manganese source, lithium source substance are mixed with solution respectively, solution mixing is mixed with carbon source material afterwards, obtains presoma with post-drying.
The second embodiment of step of the present invention (1) described mixing manganese source, lithium source and carbon source material is: manganese source or lithium source are mixed with solution, afterwards solution is mixed, and add remaining solid feed and carbon source material mixing, mix post-drying and obtain presoma.
The third embodiment of step of the present invention (1) described mixing manganese source, lithium source and carbon source material is: by manganese source, lithium source, carbon source material in solid form, obtain presoma through mechanical mixture.
Preferably, the temperature of described oven dry is 40 ~ 150 DEG C, such as 42 DEG C, 48 DEG C, 53 DEG C, 58 DEG C, 72 DEG C, 88 DEG C, 96 DEG C, 106 DEG C, 125 DEG C, 138 DEG C, 142 DEG C etc., preferably 80 DEG C.
Two of the object of the invention is to provide a kind of manganate cathode material for lithium that method prepares as described in one of object.
Three of the object of the invention is to provide a kind of lithium ion battery, and the positive pole of described lithium ion battery adopts the manganate cathode material for lithium as described in two of object.
Lithium ion battery of the present invention carries out discharge and recharge with 10C multiplying power, and circulate 500 weeks, its capability retention is 92%.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention by adding material with carbon element in LiMn2O4 raw material, and obtain the positive electrode of lithium ion battery after sintering, its specific capacity, high rate performance and cycle performance all show excellence; And the purity of manganate cathode material for lithium is high, regular particles, can meet lithium ion battery needs in actual applications;
(2) preparation method's cost of lithium ion battery mangaic acid lithium anode material provided by the invention is very low, and step is simple, and energy consumption is little, is easy to industrialization large-scale production.
Accompanying drawing explanation
Fig. 1 is gained sample LiMn in embodiment 1
2o
4x-ray powder diffraction figure;
Fig. 2 is gained sample LiMn in embodiment 1
2o
4scanning electron microscope (SEM) photograph.
Fig. 3 is gained sample LiMn in embodiment 1
2o
4high rate performance curve, the electric current put of charging under respective multiplying power is identical;
Fig. 4 is gained sample LiMn in embodiment 1
2o
4at the cyclic curve of 10C multiplying power charge and discharge.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A kind of manganate cathode material for lithium, prepares by the following method:
(1) with 50% manganese nitrate solution, lithium nitrate, water three mixing, be mixed with lithium nitrate, manganese nitrate concentration is respectively 1.6mol/L, the mixed solution of 3mol/L;
Afterwards by mixed solution described in 9mL and 3g15000 object graphite Homogeneous phase mixing, obtain mixed earth shape presoma;
Then, by described mixed earth shape presoma first 65 DEG C of heat treatment 4h in an oven, then 80 DEG C of process 1h, obtain presoma;
(2) presoma of step (1) is placed in Muffle furnace, is first warming up to 350 DEG C, constant temperature 4h, then be warming up to 700 DEG C, constant temperature 8h, is cooled to room temperature, namely obtains manganate cathode material for lithium.
Performance test:
Button cell is used to evaluate charge-discharge characteristic and the cycle performance of the manganate cathode material for lithium of the present embodiment.In performance parameter, 1C=148mA/g;
The electrochemical property test of manganate cathode material for lithium at room temperature carries out;
High rate performance test condition: test voltage scope be 3 ~ 4.5V, 0.1C discharge and recharge once, each discharge and recharge of 1C/2C/5C/10C/20C/30C/40C/50C 5 times;
Cycle performance test condition: test voltage scope 3 ~ 4.5V, carries out discharge and recharge with 10C multiplying power, circulates 500 weeks, investigates capability retention;
Electrical performance testing the results are shown in Table 1:
The electrical performance testing result of table 1 embodiment 1
As can be seen from Table 1, the ratio capacitance of the manganate cathode material for lithium that embodiment 1 provides is higher (under 0.1C multiplying power 134mAh/g), and good cycle (10C circulation keeps 92% in 500 weeks), demonstrates superior high rate performance.
Fig. 1 is the X-ray powder diffraction figure of 1 manganate cathode material for lithium provided in embodiment, and Fig. 1 shows, manganate cathode material for lithium prepared by embodiment 1 is highly purified LiMn2O4 (LiMn
2o
4), degree of crystallinity is high;
Fig. 2 is gained sample LiMn in embodiment 1
2o
4scanning electron microscope (SEM) photograph.
Fig. 3 is gained sample LiMn in embodiment 1
2o
4high rate performance curve, the electric current put of charging under respective multiplying power is identical;
Fig. 4 is gained sample LiMn in embodiment 1
2o
4at the cyclic curve of 10C multiplying power charge and discharge.
Embodiment 2:
A kind of manganate cathode material for lithium, prepares by the following method:
(1) with 50% manganese nitrate solution, lithium nitrate, water three mixing, be mixed with lithium nitrate, manganese nitrate concentration is respectively 1.6mol/L, the mixed solution of 3mol/L;
Afterwards by more than 12mL mixed solution and 3g acetylene black Homogeneous phase mixing, obtain mixed earth shape presoma;
Then, by described mixed earth shape presoma 65 DEG C of heat treatment 4h in an oven, then 80 DEG C of process 1h, obtain presoma;
(2) presoma of step (1) is placed in Muffle furnace, is first warming up to 350 DEG C, constant temperature 4h, then be warming up to 700 DEG C, constant temperature 8h, is cooled to room temperature, namely obtains manganate cathode material for lithium.
Performance test:
Method of testing is identical with embodiment 1, and electrical performance testing the results are shown in Table 2:
The electrical performance testing result of table 2 embodiment 2
As can be seen from Table 2, the ratio capacitance of the manganate cathode material for lithium that embodiment 2 provides is higher (under 0.1C multiplying power 122mAh/g), and good cycle (10C circulation keeps 88% in 500 weeks), demonstrates superior high rate performance.
Embodiment 3:
A kind of manganate cathode material for lithium, prepares by the following method:
(1) 0.6g lithium hydroxide, 3.2g manganese carbonate, 4g graphite three are added suitable alcohols and fully mix in mortar; By the mixture 200 DEG C of dry 4h in an oven obtained, obtain presoma;
(2) presoma of step (1) is placed in Muffle furnace, is first warming up to 350 DEG C, constant temperature 4h, then be warming up to 750 DEG C, constant temperature 8h, is cooled to room temperature, namely obtains manganate cathode material for lithium.
Performance test:
Method of testing is identical with embodiment 1, and electrical performance testing the results are shown in Table 3:
The electrical performance testing result of table 3 embodiment 3
As can be seen from Table 3, the ratio capacitance of the manganate cathode material for lithium that embodiment 3 provides is higher (under 0.1C multiplying power 129mAh/g), and good cycle (10C circulation keeps 90% in 500 weeks), demonstrates superior high rate performance.
Embodiment 4:
A kind of manganate cathode material for lithium, prepares by the following method:
(1) 6.77g tetra-hydration manganese acetate, 1.58g bis-hydration lithium acetate being successively dissolved in 20mL temperature is (mol ratio Li:Mn=1.12:2) in the deionized water of 90 DEG C, then 6g graphite is added wherein, be uniformly mixed with magnetic, 90 DEG C of water-bath 5h, then 110 DEG C of baking 10h obtain presoma in an oven;
(2) presoma of step (1) is placed in Muffle furnace, is first warming up to 350 DEG C, constant temperature 4h, then be warming up to 750 DEG C, constant temperature 8h, is cooled to room temperature, namely obtains manganate cathode material for lithium.
Performance test:
Method of testing is identical with embodiment 1, and electrical performance testing the results are shown in Table 4:
The electrical performance testing result of table 4 embodiment 4
As can be seen from Table 4, the ratio capacitance of the manganate cathode material for lithium that embodiment 4 provides is higher (under 0.1C multiplying power 118mAh/g), and good cycle (10C circulation keeps 94% in 500 weeks), demonstrates superior high rate performance.
Embodiment 5:
A kind of manganate cathode material for lithium, prepares by the following method:
(1) with 50% manganese nitrate solution, lithium nitrate, water three mixing, be mixed with lithium nitrate, manganese nitrate concentration is respectively 1.6mol/L, the mixed solution of 3mol/L;
Afterwards by mixed solution described in 10mL and 5g800 object graphite Homogeneous phase mixing, obtain mixed earth shape presoma;
Then, by described mixed earth shape presoma first 65 DEG C of heat treatment 4h in an oven, then 80 DEG C of process 1h, obtain presoma;
(2) presoma of step (1) is placed in Muffle furnace, is first warming up to 350 DEG C, constant temperature 4h, then be warming up to 700 DEG C, constant temperature 8h, is cooled to room temperature, namely obtains manganate cathode material for lithium.
Performance test:
Method of testing is identical with embodiment 1, and electrical performance testing the results are shown in Table 5:
The electrical performance testing result of table 5 embodiment 5
As can be seen from Table 5, the ratio capacitance of the manganate cathode material for lithium that embodiment 5 provides is higher (under 0.1C multiplying power 135mAh/g), and good cycle (10C circulation keeps 91% in 500 weeks), demonstrates superior high rate performance.
Comparative example 1
Only be with the difference of embodiment 1: do not add graphite.
Comparative example 2
Only be with the difference of embodiment 1: step (2) is directly warming up to 750 DEG C of constant temperature 8h in Muffle furnace.
Comparative example 3
Be with the difference of embodiment 1: in step (1), the addition of carbon is 0.4g.
Comparative example 4
Be with the difference of embodiment 1: in step (1), the addition of carbon is 30g.
Performance test:
Method of testing is identical with embodiment 1, and electrical performance testing the results are shown in Table 6:
The electrical performance testing result of table 6 comparative example
As can be seen from Table 6, the present invention by add in LiMn2O4 raw material material with carbon element play dispersant, can the effect of ablation template, after sintering, the microstructure of manganate cathode material for lithium is changed, obtain the positive electrode that specific capacity, high rate performance and cycle performance all show excellent lithium ion battery, and material with carbon element self is oxidized to carbon dioxide in atmosphere and removes.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for manganate cathode material for lithium, is characterized in that, described method comprises the steps:
(1) mix manganese source, lithium source and carbon source material, obtain presoma;
(2) presoma of step (1) is sintered in atmosphere, after cooling, obtain manganate cathode material for lithium.
2. preparation method as claimed in claim 1, it is characterized in that, in described presoma, the mol ratio of manganese element and elemental lithium is 2:1 ~ 1.2;
Preferably, in described presoma, the mol ratio of manganese element and carbon is 0.025 ~ 0.5:1, preferred 0.14:1.
3. preparation method as claimed in claim 1 or 2, it is characterized in that, step is sintered to described in (2): first carry out once sintered at 150 ~ 450 DEG C, carry out double sintering at being then warmed up to 550 ~ 850 DEG C;
Preferably, step (2) the described once sintered time is 1 ~ 10h;
Preferably, step (2) the described double sintering time at more than 1h, preferably 1 ~ 48h;
Preferably, step (2) described sintering carries out in Muffle furnace.
4. the preparation method as described in one of claims 1 to 3, is characterized in that, step is sintered to described in (2): first at 350 DEG C, carry out once sintered 4h, carry out double sintering 8h at being then warmed up to 700 DEG C.
5. the preparation method as described in one of Claims 1 to 4, is characterized in that, described carbon source material is selected from the combination of any a kind or at least 2 kinds in carbon black, graphite, carbon nano-tube, active carbon;
Preferably, described carbon black is conductive carbon black, preferably includes the combination of any a kind or at least 2 kinds in acetylene black, ECP600JD, superpli, KS-6;
Further preferably, described carbon source material is graphite and/or acetylene black.
6. the preparation method as described in one of Claims 1 to 5, it is characterized in that, described manganese source is the combination of any a kind or at least 2 kinds in manganous bromide, manganese carbonate, manganese chloride, manganese oxide, manganese nitrate, manganese oxalate, manganese sulfate, manganese acetate, preferred manganese nitrate and/or manganese acetate;
Preferably, described lithium source is the combination of any a kind or at least 2 kinds in lithium carbonate, lithium hydroxide, lithia, lithium oxalate, lithium acetate, lithium nitrate, preferred lithium nitrate and/or lithium acetate.
7. the preparation method as described in one of claim 1 ~ 6, it is characterized in that, the mode of step (1) described mixing manganese source, lithium source and carbon source material is: manganese source, lithium source are mixed with solution respectively, solution mixing is mixed with carbon source material afterwards, obtains presoma with post-drying;
Or the mode of step (1) described mixing manganese source, lithium source and carbon source material is: manganese source or lithium source are mixed with solution, afterwards solution is mixed, and add remaining solid feed and carbon source material mixing, mix post-drying and obtain presoma;
Or the mode of step (1) described mixing manganese source, lithium source and carbon source material is: by manganese source, lithium source, carbon source material in solid form, obtain presoma through mechanical mixture;
Preferably, the temperature of described oven dry is 40 ~ 150 DEG C, preferably 80 DEG C.
8. the manganate cathode material for lithium that method prepares as described in one of claim 1 ~ 7.
9. a lithium ion battery, is characterized in that, the positive pole of described lithium ion battery adopts manganate cathode material for lithium as claimed in claim 8.
10. lithium ion battery as claimed in claim 9, it is characterized in that, described lithium ion battery carries out discharge and recharge with 10C multiplying power, and circulate 500 weeks, its capability retention is 92%.
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| CN107104233A (en) * | 2017-05-26 | 2017-08-29 | 国家纳米科学中心 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109292826A (en) * | 2018-07-26 | 2019-02-01 | 华南理工大学 | A kind of porous lithium manganate material of high charge-discharge capacity and preparation method and application |
| CN109786695A (en) * | 2018-12-29 | 2019-05-21 | 合肥融捷能源材料有限公司 | A kind of high magnification nickel-cobalt lithium manganate cathode material and preparation method thereof |
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| CN105753072A (en) * | 2016-02-03 | 2016-07-13 | 国家纳米科学中心 | Lithium nickel manganese oxide as well as preparation method and application thereof |
| CN106450281A (en) * | 2016-11-10 | 2017-02-22 | 桂林理工大学 | Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping |
| CN106972171B (en) * | 2017-05-08 | 2020-06-30 | 国家纳米科学中心 | Three-dimensional network structure material, preparation method and application thereof |
| CN106972171A (en) * | 2017-05-08 | 2017-07-21 | 国家纳米科学中心 | A kind of three-dimensional net structure material, preparation method and its usage |
| CN107104233A (en) * | 2017-05-26 | 2017-08-29 | 国家纳米科学中心 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109292826B (en) * | 2018-07-26 | 2020-12-22 | 华南理工大学 | Porous lithium manganate material with high charge-discharge capacity, and preparation method and application thereof |
| CN109292826A (en) * | 2018-07-26 | 2019-02-01 | 华南理工大学 | A kind of porous lithium manganate material of high charge-discharge capacity and preparation method and application |
| CN109786695A (en) * | 2018-12-29 | 2019-05-21 | 合肥融捷能源材料有限公司 | A kind of high magnification nickel-cobalt lithium manganate cathode material and preparation method thereof |
| CN109786695B (en) * | 2018-12-29 | 2022-01-28 | 合肥融捷能源材料有限公司 | High-rate lithium nickel cobalt manganese oxide positive electrode material and preparation method thereof |
| CN110156086A (en) * | 2019-03-29 | 2019-08-23 | 中国电力科学研究院有限公司 | A kind of preparation method of manganate cathode material for lithium |
| CN111426184A (en) * | 2020-03-13 | 2020-07-17 | 晋江云智新材料科技有限公司 | Continuous electric heating rotary furnace and process for preparing lithium manganate by adopting same |
| CN111426184B (en) * | 2020-03-13 | 2022-03-25 | 福建省云智新材料科技有限公司 | Continuous electric heating rotary furnace and process for preparing lithium manganate by adopting same |
| CN114684866A (en) * | 2020-12-25 | 2022-07-01 | 三明市新能源产业技术研究院有限公司 | Nickel-cobalt-manganese ternary material and preparation method thereof and lithium ion battery |
| CN112897585A (en) * | 2021-02-01 | 2021-06-04 | 山东海科创新研究院有限公司 | Spinel lithium manganate, preparation method thereof and lithium ion battery |
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