CN110416516A - A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide - Google Patents

A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide Download PDF

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Publication number
CN110416516A
CN110416516A CN201910674842.8A CN201910674842A CN110416516A CN 110416516 A CN110416516 A CN 110416516A CN 201910674842 A CN201910674842 A CN 201910674842A CN 110416516 A CN110416516 A CN 110416516A
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coal
anode
ion battery
lithium
preparation
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尹华意
李翌珂
李亚戈
郭锦雯
齐子韬
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/21—Manganese oxides
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, belongs to field of batteries.It should be the preparation method comprises the following steps: preparing coal dust and manganese monoxide composite material or coal dust and manganous hydroxide composite material；By the composite material preforms, as cathode of composite material；It after sodium carbonate and potassium carbonate dehydrating and removing impurities, is passed through argon gas and is warming up to fused salt fusing point, then heat up, preelectrolysis is carried out using foam nickel cathode, then cathode of composite material is inserted into fused salt and is electrolysed, decomposition voltage is 1.8V~2.8V, and electrolysis time is 1~12h；Cathode of composite material product cleaning after electrolysis is dry, obtain the anode material of lithium-ion battery of coal and manganese monoxide.The sodium-ion battery coulombic efficiency of negative electrode material preparation is up to 98%~105%.This method obtains the anode material of lithium-ion battery of function admirable using high temperature fused salt electrolysis method, has raw material sources extensive, environmentally friendly, cost is relatively low, simple operation and other advantages.

Description

A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide
Technical field
The present invention relates to field of batteries, and in particular to a kind of preparation of the anode material of lithium-ion battery of coal and manganese monoxide Method.
Background technique
Battery is a kind of device that chemical energy can be converted to electric energy as a kind of traditional energy storage material.Battery is as energy The advantages of measuring source, there is output voltage, electric current to stablize, and long-time stable is powered, and battery structure is simple, it is easy to carry, it fills Discharge operation is simple and easy to do, and the influence vulnerable to outside climatic and temperature, not stable and reliable for performance, plays in modern society's life Great function.Current battery negative electrode material mainly has graphite, soft carbon (such as coke), hard carbon, the negative electrode material explored There are nitride, PAS, tin-based oxide, tin alloy, nanometer anode material, and other some intermetallic compounds etc., at present It is most widely used still to surely belong to carbon material.
Lithium ion battery is one of current most widely used battery, using the problem of be: limited capacity and cost Higher, compared with lithium ion battery, sodium-ion battery has had the advantage that sodium-ion battery: sodium salt raw material rich reserves, valence Lattice are cheap.Characteristic possessed by sodium salt allows sodium-ion battery to use low concentration electrolyte, can further reduce the cost；It is existing The negative electrode material that uses of sodium-ion battery have carbon-based material, non-metal simple-substance, organic compound, metal oxide, these are negative In the material of pole, the shortcomings that generally existing capacity of carbon-based material is low, poor circulation, non-metal simple-substance coulombic efficiency and cycle performance Unexcellent, the irreversible specific capacity of electrode made from organic compound is larger, and metal oxide can use compound with carbon material, carbon The addition of material effectively increases the specific capacity of material, improves cycle performance, and carbon material has been buffered very well during sodium deintercalation The volume change of metal oxide, and it can be used as conductive media, it can significantly solve the problems, such as that its performance is poor, and it is existing at present Carbon/manganese composite material is the compound of manganese dioxide or manganese monoxide and carbon, and the preparation method used is at high price, is operated numerous It is trivial, height is required to practical operation, therefore, so that the preparation cost of sodium-ion battery increases.
Summary of the invention
The purpose of the present invention is the preparation methods in a kind of coal and the anode material of lithium-ion battery of manganese monoxide.This method Using coal dust as carbon source, after mixing with bivalent manganese source, as the presoma of reaction, tabletting obtains composite material preforms, spare.With carbon The fused salt mixt of sour sodium and potassium carbonate is reaction medium, and nickel-base alloy is inert anode, and composite material preforms are cathode, is being located in advance It is reacted in the 750 DEG C of high-temperature molten salts managed by potentiostatic deposition, changes the performance of composite material preforms, then by composite material Tabletting lift-off fused salt is cooling, cleans, is dry, obtains cathode product as anode material of lithium-ion battery.Method of the invention is adopted The anode material of lithium-ion battery of function admirable can be made with high temperature fused salt electrolysis method, have raw material sources extensive, to environment Close friend, cost is relatively low, simple operation and other advantages.
The purpose of the present invention is the preparation methods in a kind of coal and the anode material of lithium-ion battery of manganese monoxide, including with Lower step:
Step 1: the preparation of dopant material
Prepare the composite material of coal dust and bivalent manganese source；Wherein, in composite material, in molar ratio, coal dust: in bivalent manganese source Mn2+=1:(1~10)；Wherein, bivalent manganese source is manganese monoxide or manganous hydroxide；
Step 2: preparing
(1) by the composite material preforms of coal dust and bivalent manganese source, composite material preforms are obtained；
(2) composite material preforms are fixed on stainless steel wire collector with iron wire, as cathode of composite material；By foam Nickel is fixed on stainless steel wire collector with iron wire, foam nickel cathode when as preelectrolysis；By nickel-base alloy and stainless steel wire Collector connection, as anode；
(3) sodium carbonate and potassium carbonate are sufficiently mixed, are placed in crucible, then crucible is placed in reactor, capping Device vacuumizes and is warming up to 450~550 DEG C, and keeps the temperature 10~15h, carries out dehydrating and removing impurities processing, the carbon after obtaining dehydrating and removing impurities Hydrochlorate；Wherein, by molar content, sodium carbonate is 45~70mol%, and potassium carbonate is 55~30mol%, preferably, carbonic acid Sodium: potassium carbonate=59mol%:41mol%；
(4) above carbonate after cathode of composite material, foam nickel cathode, anode to be suspended in dehydrating and removing impurities, to anti- It answers and is continually fed into argon gas in device, so that forming argon atmosphere in reactor；
Step 3: preelectrolysis
After the fusion temperature of carbonate after reactor to be heated to dehydrating and removing impurities, fused salt is formed, reaction is then heated to Temperature；By in foam nickel cathode, anode insertion fused salt, applies voltage at foam nickel cathode, anode both ends, carry out preelectrolysis, in advance After electrolysis, foam nickel cathode is taken out from fused salt；Fusing temperature of the reaction temperature than the carbonate after dehydrating and removing impurities It spends 40 ± 5 DEG C high；
Step 4: electrolysis
Cathode of composite material is inserted into fused salt and is electrolysed, applies voltage in cathode of composite material and anode both ends, into Row constant-potential electrolysis, the cathode of composite material product after being electrolysed；Wherein, decomposition voltage is 1.8V~2.8V, electrolysis time For 1~12h；
Step 5: post-processing
Cathode of composite material product after electrolysis is taken out from fused salt, cooling, cleaning removal fused salt is dry, obtain coal with The anode material of lithium-ion battery of manganese monoxide.
In the step 1, the composite material of coal dust and bivalent manganese source is prepared, preparation method is using in following two It is a kind of:
The first: the composite material of coal dust and manganese monoxide
According to raw material proportioning in composite material, after coal dust and manganese monoxide are ground, ball milling mixing, sieves, obtain coal dust With the composite material of manganese monoxide, average diameter < 0.1mm of the composite material of coal dust and manganese monoxide；
Second: the composite material of coal dust and manganous hydroxide
According to raw material proportioning in composite material, soluble manganous salt, consumption of oxalic acid are calculated, by coal dust, oxalic acid, solubility The aqueous solution of manganous salt mixes, and obtains mixed liquor, is stirred to react to liquid internal uniformly without obvious layering, is separated by solid-liquid separation, will After solid product drying, obtain the composite material of coal dust and manganous hydroxide, the composite material of coal dust and manganous hydroxide it is average straight Diameter < 0.1mm.
In the method for the above-mentioned composite material for preparing coal dust and bivalent manganese source, the grinding, preferably mortar grinder, more Preferably ceramic mortar.The screening is 150 mesh sieve, aperture 0.1mm.
Described is stirred to react to liquid internal uniformly without the time being obviously layered, preferably 5~7h.
The mass concentration of the oxalic acid is preferably 0.5~2mol/L.
The separation of solid and liquid is preferably filtered or is centrifuged, and is that suction filtration point is carried out using 0.45 μm of filter membrane when using filtering From.
The drying, using being placed in a vacuum drying oven in 60~90 DEG C of 10~15h of drying.
The soluble manganous salt is preferably manganese chloride.
In the step 2 (1), tablet forming technique is that tableting pressure is 2~4MPa, and the dwell time is 0.5~2min.
In the step 2 (2), quality purity >=99.9wt.% of the nickel foam；The diameter of the iron wire is 0.3±0.01mm；The diameter of the stainless steel wire collector is 2.0 ± 0.1mm.
In the step 2 (2), nickel-base alloy is preferably ambrose alloy ferroalloy.
In the step 2 (3), the technique of dehydrating and removing impurities processing are as follows: sodium carbonate and potassium carbonate are placed in reactor, it will Reactor vacuumizes, and is warming up to 450~550 DEG C, is 10Pa in vacuum pressure, dry 10~15h.In the process, carbonic acid Sodium and potassium carbonate while evaporating moisture and removing with the progress of temperature-rise period.
In the step 2 (4), it is continually fed into argon gas into reactor under ambient pressure, argon gas is from reactor air inlet It mouthful is passed through, is discharged from reactor gas outlet, when discharge, the moisture and impurity of sodium carbonate and the mixed carbonate of potassium carbonate are by argon Gas is taken away.
In the step 3, preelectrolysis voltage is 1.8V~2.2V, and the preelectrolysis time is 1~3h；The purpose of preelectrolysis is Removing may mixed impurity in fused salt in reactor.
In the step 4, electrolysis temperature is 30 DEG C~50 DEG C higher than fused salt fusion temperature, and preferably 750 ± 10 DEG C.
The anode material of lithium-ion battery of coal and manganese monoxide prepared by the present invention, is grain structure, partial size < 100 μm, For the mixture of carbon and sub- manganese.
A kind of anode material of lithium-ion battery of coal and manganese monoxide is made using above-mentioned preparation method.
A kind of sodium-ion battery, the anode material of lithium-ion battery including coal obtained above and manganese monoxide, preparation Sodium-ion battery coulombic efficiency is up to 98%~105%.
A kind of preparation method of the anode material of lithium-ion battery of of the invention coal and manganese monoxide, principle is by coal dust It is sufficiently mixed rear tabletting with bivalent manganese source (manganese monoxide or manganous hydroxide), changes coal in high-temperature molten salt in the method for electrochemistry Mealiness energy removes impurity, changes the structure feature of carbon, in the anode material of lithium-ion battery for making coal and manganese monoxide, the hole of coal Gap increases, and convenient for discrepancy of the sodium ion in charge and discharge process, and manganous hydroxide therein is prepared into manganese monoxide, being made property The excellent anode material of lithium-ion battery of energy.
The method that a kind of high temperature fused salt electrolysis coal and manganese monoxide of the invention prepares anode material of lithium-ion battery, has Beneficial effect is:
1, anode material of lithium-ion battery made from method of the invention has raw material sources extensive, easy to operate, to ring The features such as border is friendly, cost is relatively low, easy to operate.
2, the present invention is restored with electrochemical method and coal dust and manganese monoxide is made, and is that the obtained performance of electrolysis is excellent in fused salt The anode material of lithium-ion battery of good coal dust and manganese monoxide is conducive to improve carbon surface structure, so that composite material is in electricity It is more efficient in terms of the conduction energy storage of pond, it is economical.
3, the present invention using carbonate as fused salt, in last handling process, removal easy to clean.
4, anode material of lithium-ion battery prepared by the present invention can be prepared using manganese monoxide or manganese salt, be made Standby anode material of lithium-ion battery low cost can also stablize charge/discharge capacity, stability after cycle efficieny reaches 100 circles Height is directly to adulterate mineral coal and manganese monoxide, and the sodium-ion battery for meeting application performance is made in high temperature fused salt electrolysis Negative electrode material.
Detailed description of the invention
Fig. 1 is the process flow signal of the preparation method of the anode material of lithium-ion battery of coal and manganese monoxide of the invention Figure.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
In following instance, unless specifically indicated, the raw material and equipment of use be it is commercially available, purity be analyze it is pure or more, Specifically:
Feed coal uses Datong high-quality coal, is commercial products, wherein carries out Eds to Datong high-quality coal Analysis, obtains the mass percent of the ingredient contained in the high-quality coal of Datong and each ingredient are as follows: O is 10~20%, remaining Amount is C and inevitable impurity, total content≤1% of impurity.The nickel foam that uses, thin wire, stainless steel wire is commercially available productions Product.The agate mortar that uses, ceramic mortar, corundum crucible is commercial products.The salt used is for sodium carbonate, potassium carbonate, purity It analyzes pure.The nickel-base alloy electrode used is made products.
In following embodiment, the nickel foam purity used is 99.9wt.%.The manganese monoxide purity used is pure to analyze； The concentration of oxalic acid used is 1mol/L.The diameter of the thin wire of use is in 0.3 ± 0.01mm, purity 99.99%.What is used is stainless Gauge of wire is in 2.0 ± 0.1mm, model 304.
In following embodiment, the fused salt operation temperature control of sodium carbonate, potassium carbonate is at 750 ± 5 DEG C.Apply between two electrodes Voltage range be 1.8 ± 0.1V~2.8 ± 0.1V.The D.C. regulated power supply model of use are as follows: WYJ40A15V.
In following embodiment, the gas outlet of reactor extends to the lower section of the pond liquid level outside reactor by pipeline, When argon gas persistently circulates, there is bubble to emerge.Moisture removal and impurity is gone to be put in reactor in sodium carbonate, potassium carbonate, in temperature Dry 12h under the conditions of 500 DEG C and vacuum environment.Carrying out heating to the material in reactor is that reactor is placed in resistance wire furnace Heating.
Embodiment 1
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, process flow chart are shown in Fig. 1, by with Lower step carries out:
Step 1: the preparation of dopant material
(1) Datong 0.5g high-quality coal is weighed in the balance, 0.5g manganese monoxide, by the two hammer fritter hammer out, Mixing fritter is placed in ceramic mortar and is clayed into power, and is put in ball milling in ball mill, is sieved, coal dust and manganese monoxide are obtained Composite material；Wherein, the average diameter of the composite material of coal dust and manganese monoxide is 0.09mm；
Step 2: preparing before electrolysis
(1) composite material for weighing coal dust and manganese monoxide in 1g step 1 in the balance, with tablet press machine at 4MPa, pressure maintaining 2min obtains composite material preforms；
(2) composite material preforms are tied up with 0.3mm ± 0.01mm iron wire in 2mm ± 0.1mm304 stainless steel wire collector On, cathode of composite material is made；Nickel foam is tied up with 0.3mm ± 0.01mm iron wire in 2mm ± 0.1mm304 stainless steel wire afflux On body, foam nickel cathode is made；Nickel-base alloy is connect with 2mm ± 0.1mm304 stainless steel wire collector, and anode is made；
(3) by sodium carbonate: potassium carbonate=59:41 (mol%) weighs 700g salt-mixture, wherein sodium carbonate 367.51g, Potassium carbonate is 332.49g, is placed in ceramic mortar and is sufficiently mixed, then pours into corundum crucible and be placed in reactor；Closing Reactor, when vacuumizing reactor while after being heated to 500 DEG C, dry 12h carries out dehydrating and removing impurities processing, is dehydrated The salt-mixture of sodium carbonate and potassium carbonate after removal of impurities.
(4) by cathode of composite material, foam nickel cathode, nickel-base alloy anode be suspended in the sodium carbonate after dehydrating and removing impurities and Above the salt-mixture of potassium carbonate, in the case where pressure is ambient pressure conditions, it is continually fed into argon gas to reactor, so that shape in reactor At argon atmosphere；
Step 3: preelectrolysis
Reactor is heated to 750 ± 10 DEG C, the salt-mixture of sodium carbonate and potassium carbonate is made to melt to form fused salt, heating process Moisture and impurity in middle fused salt are taken away by argon gas；By in foam nickel cathode, nickel-base alloy anode insertion fused salt, in cathode and Anode both ends apply 2.0V voltage, carry out constant-potential electrolysis 2h, then propose foam nickel cathode.
Step 4: electrolysis
Cathode of composite material is inserted into fused salt and is electrolysed, applies voltage in cathode of composite material and anode both ends, into Row constant-potential electrolysis, obtains cathode product；Wherein, voltage 1.8V, electrolysis time 3h, obtains cathode product.
Step 5: post-processing
Cathode product is taken out from fused salt, it is cooling, it is put into deionized water, removing fused salt is cleaned multiple times, is obtained after dry The anode material of lithium-ion battery of coal and manganese monoxide, encapsulation.
Using the anode material of lithium-ion battery of coal and manganese monoxide as anode material of lithium-ion battery, assembling obtain sodium from Sub- battery.The sodium-ion battery is tested, after cycle charge-discharge 100 encloses, coulomb compares up to 102%, and capacity is reachable 80mAh/g。
Embodiment 2
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 3
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 4
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.0V voltage at anode and cathode both ends；Other modes are identical.
Embodiment 5
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.0V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；Other modes are identical.
Embodiment 6
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.0V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；Other modes are identical.
Embodiment 7
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.2V voltage at anode and cathode both ends；Other modes are identical.
Embodiment 8
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.2V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；Other modes are identical.
Embodiment 9
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.2V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；Other modes are identical.
Embodiment 10
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.4V voltage at anode and cathode both ends；Other modes are identical.
Embodiment 11
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.4V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；Other modes are identical.
Embodiment 12
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.4V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；Other modes are identical.
Embodiment 13
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.6V voltage at anode and cathode both ends；Other modes are identical.
Embodiment 14
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.6V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；Other modes are identical.
Embodiment 15
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.6V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；Other modes are identical.
Embodiment 16
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.7V voltage at anode and cathode both ends；Other modes are identical.
Embodiment 17
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.7V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；Other modes are identical.
Embodiment 18
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.7V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；Other modes are identical.
Embodiment 19
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.8V voltage at anode and cathode both ends；Other modes are identical.
Embodiment 20
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.8V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；Other modes are identical.
Embodiment 21
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) in step 4 electrolytic process, apply 2.8V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；Other modes are identical.
Embodiment 22
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；Other modes are identical.
Embodiment 23
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, electrolysis time 5h；Other modes phase Together.
Embodiment 24
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, electrolysis time 8h；Other modes phase Together.
Embodiment 25
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.0V electricity at anode and cathode both ends Pressure；Other modes are identical.
Embodiment 26
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.0V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 27
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.0V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 28
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.2V electricity at anode and cathode both ends Pressure；Other modes are identical.
Embodiment 29
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.2V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 30
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.2V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 31
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.4V electricity at anode and cathode both ends Pressure；Other modes are identical.
Embodiment 32
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.4V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 33
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.4V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 34
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.6V electricity at anode and cathode both ends Pressure；Other modes are identical.
Embodiment 35
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.6V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 36
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.6V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 37
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.7V electricity at anode and cathode both ends Pressure；Other modes are identical.
Embodiment 38
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) step manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply at anode and cathode both ends 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 39
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.7V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 40
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.8V electricity at anode and cathode both ends Pressure；Other modes are identical.
Embodiment 41
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.8V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 42
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 1g；(2) in step 4 electrolytic process, apply 2.8V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 43
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；Other modes are identical.
Embodiment 44
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, electrolysis time 5h；Other modes It is identical.
Embodiment 45
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, electrolysis time 8h；Other modes It is identical.
Embodiment 46
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.0V at anode and cathode both ends Voltage；Other modes are identical.
Embodiment 47
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.0V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 48
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.0V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 49
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.2V at anode and cathode both ends Voltage；Other modes are identical.
Embodiment 50
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.2V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 51
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.2V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 52
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.4V at anode and cathode both ends Voltage；Other modes are identical.
Embodiment 53
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.4V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 54
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.4V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 55
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.6V at anode and cathode both ends Voltage；Other modes are identical.
Embodiment 56
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.6V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 57
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.6V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 58
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.7V at anode and cathode both ends Voltage；Other modes are identical.
Embodiment 59
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.7V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 60
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.7V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 61
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.8V at anode and cathode both ends Voltage；Other modes are identical.
Embodiment 62
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.8V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Embodiment 63
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 2.5g；(2) in step 4 electrolytic process, apply 2.8V at anode and cathode both ends Voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 64
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；Other modes are identical.
Embodiment 65
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, electrolysis time 5h；Other modes phase Together.
Embodiment 66
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 67
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.0V electricity at anode and cathode both ends Pressure；
Other modes are identical.
Embodiment 68
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.0V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 69
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.0V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 70
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.2V electricity at anode and cathode both ends Pressure；
Other modes are identical.
Embodiment 71
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.2V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 72
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.2V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 73
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.4V electricity at anode and cathode both ends Pressure；
Other modes are identical.
Embodiment 74
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.4V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 75
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.4V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 76
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.6V electricity at anode and cathode both ends Pressure；
Other modes are identical.
Embodiment 77
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.6V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 78
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.6V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 79
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.7V electricity at anode and cathode both ends Pressure；
Other modes are identical.
Embodiment 80
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.7V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 81
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.7V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 82
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.8V electricity at anode and cathode both ends Pressure；
Other modes are identical.
Embodiment 83
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.8V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 84
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 1, difference is:
(1) manganese monoxide takes 0.5g, and coal dust takes 5g；(2) in step 4 electrolytic process, apply 2.8V electricity at anode and cathode both ends Pressure；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 85
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, process flow chart are shown in Fig. 1, by with Lower step carries out:
Step 1: the preparation of dopant material
Weigh the manganese chloride of 0.5g in the balance, it is soluble in water, it weighs 0.5 coal dust in the balance, is added to manganese chloride aqueous solution In, 10mL oxalic acid solution is added and stirs evenly, is filtered using 0.45 μm of filter membrane, after solid matter is dried, obtains coal dust With the composite material of manganous hydroxide；
Step 2: preparing before electrolysis
(1) composite material for weighing the coal dust and manganous hydroxide in 1g step 1 in the balance is protected with tablet press machine at 4MPa 2min is pressed, composite material preforms are obtained；
(2) composite material preforms are tied up with 0.3mm ± 0.01mm iron wire in 2mm ± 0.1mm304 stainless steel wire collector On, cathode of composite material is made；Nickel foam is tied up with 0.3mm ± 0.01mm iron wire in 2mm ± 0.1mm304 stainless steel wire afflux On body, foam nickel cathode is made；Nickel-base alloy is connect with 2mm ± 0.1mm304 stainless steel wire collector, and anode is made；
(3) by sodium carbonate: potassium carbonate=59:41 (mol%) weighs 700g salt-mixture, wherein sodium carbonate 367.51g, Potassium carbonate is 332.49g, is placed in ceramic mortar and is sufficiently mixed, then pours into corundum crucible and be placed in reactor；Closing is anti- Device is answered, reactor is vacuumized, at 460 DEG C, pressure 10Pa, dry 12h carries out dehydrating and removing impurities processing, after obtaining dehydrating and removing impurities Sodium carbonate and potassium carbonate salt-mixture.
(4) by cathode of composite material, foam nickel cathode, nickel-base alloy anode be suspended in the sodium carbonate after dehydrating and removing impurities and Above the salt-mixture of potassium carbonate, under ambient pressure, it is continually fed into argon gas to reactor, so that forming argon gas gas in reactor Atmosphere；
Step 3: preelectrolysis
Reactor is heated to 750 ± 10 DEG C, the salt-mixture of sodium carbonate and potassium carbonate is made to melt to form fused salt, heating process Moisture and impurity in middle fused salt are taken away by argon gas；Foam nickel cathode, nickel-base alloy anode are inserted into fused salt, in anode and cathode Both ends apply 2.0V voltage, carry out constant-potential electrolysis 2h, then propose foam nickel cathode.
Step 4: electrolysis
Cathode of composite material is inserted into fused salt and is electrolysed, applies voltage in cathode of composite material and anode both ends, into Row constant-potential electrolysis, obtains cathode product；Wherein, voltage 1.8V, electrolysis time 3h, obtains cathode product.
Step 5: post-processing
Cathode product is taken out from fused salt, it is cooling, it is put into deionized water, removing fused salt is cleaned multiple times, is obtained after dry The anode material of lithium-ion battery of coal and manganese monoxide, encapsulation.
The anode material of lithium-ion battery of coal and manganese monoxide is used for sodium-ion battery.
Embodiment 86
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 87
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 88
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.0V voltage at anode and cathode both ends；
Other modes are identical.
Embodiment 89
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.0V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；
Other modes are identical.
Embodiment 90
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.0V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；
Other modes are identical.
Embodiment 91
The preparation method of the anode material of lithium-ion battery of a kind of coal and manganese monoxide, with embodiment 85, difference It is:
(1) in step 4 electrolytic process, apply 2.2V voltage at anode and cathode both ends；
Other modes are identical.
Embodiment 92
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.2V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；
Other modes are identical.
Embodiment 93
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.2V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；
Other modes are identical.
Embodiment 94
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.4V voltage at anode and cathode both ends；
Other modes are identical.
Embodiment 95
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.4V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；
Other modes are identical.
Embodiment 96
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.4V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；
Other modes are identical.
Embodiment 97
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.6V voltage at anode and cathode both ends；
Other modes are identical.
Embodiment 98
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.6V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；
Other modes are identical.
Embodiment 99
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.6V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；
Other modes are identical.
Embodiment 100
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.7V voltage at anode and cathode both ends；
Other modes are identical.
Embodiment 101
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.7V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；
Other modes are identical.
Embodiment 102
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.7V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；
Other modes are identical.
Embodiment 103
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.8V voltage at anode and cathode both ends；
Other modes are identical.
Embodiment 104
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.8V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 5h；
Other modes are identical.
Embodiment 105
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) in step 4 electrolytic process, apply 2.8V voltage at anode and cathode both ends；(2) in step 4 electrolytic process, when electrolysis Between be 8h；
Other modes are identical.
Embodiment 106
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；
Other modes are identical.
Embodiment 107
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, electricity The solution time is 5h；
Other modes are identical.
Embodiment 108
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, electricity The solution time is 8h；
Other modes are identical.
Embodiment 109
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；
Other modes are identical.
Embodiment 110
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 111
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 112
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；
Other modes are identical.
Embodiment 113
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 114
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 115
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；
Other modes are identical.
Embodiment 116
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 117
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 118
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；
Other modes are identical.
Embodiment 119
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 120
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 121
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；
Other modes are identical.
Embodiment 122
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 123
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 124
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；
Other modes are identical.
Embodiment 125
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 126
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 1.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 127
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；
Other modes are identical.
Embodiment 128
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, electricity The solution time is 5h；
Other modes are identical.
Embodiment 129
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, electricity The solution time is 8h；
Other modes are identical.
Embodiment 130
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；
Other modes are identical.
Embodiment 131
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 132
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 133
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；
Other modes are identical.
Embodiment 134
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 135
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 136
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；
Other modes are identical.
Embodiment 137
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 138
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 139
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；
Other modes are identical.
Embodiment 140
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 141
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 142
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；
Other modes are identical.
Embodiment 143
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 144
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 145
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；
Other modes are identical.
Embodiment 146
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；
Other modes are identical.
Embodiment 147
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 2.5g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；
Other modes are identical.
Embodiment 148
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；
Other modes are identical.
Embodiment 149
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, electricity The solution time is 5h；Other modes are identical.
Embodiment 150
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, electricity The solution time is 8h；Other modes are identical.
Embodiment 151
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；Other modes are identical.
Embodiment 152
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 153
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.0V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 154
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；Other modes are identical.
Embodiment 155
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 156
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.2V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 157
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；Other modes are identical.
Embodiment 158
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 159
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.4V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 160
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；Other modes are identical.
Embodiment 161
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 162
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.6V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 163
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；Other modes are identical.
Embodiment 164
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 165
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.7V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.
Embodiment 166
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；Other modes are identical.
Embodiment 167
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；(3) in step 4 electrolytic process, electrolysis time 5h；Other modes are identical.
Embodiment 168
A kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, with embodiment 85, difference is:
(1) manganese chloride of 0.5g and the coal dust of 5.0g are taken when the dopant material of step 1；(2) in step 4 electrolytic process, In Anode and cathode both ends apply 2.8V voltage；(3) in step 4 electrolytic process, electrolysis time 8h；Other modes are identical.

Claims (10)

1. a kind of preparation method of the anode material of lithium-ion battery of coal and manganese monoxide, which comprises the following steps:
Step 1: the preparation of dopant material
Prepare the composite material of coal dust and bivalent manganese source；Wherein, in composite material, in molar ratio, coal dust: Mn in bivalent manganese source2+ =1:(1~10)；Wherein, bivalent manganese source is manganese monoxide or manganous hydroxide；
Step 2: preparing
(1) by the composite material preforms of coal dust and bivalent manganese source, composite material preforms are obtained；
(2) composite material preforms are fixed on stainless steel wire collector with iron wire, as cathode of composite material；Nickel foam is used Iron wire is fixed on stainless steel wire collector, foam nickel cathode when as preelectrolysis；By nickel-base alloy and stainless steel wire afflux Body connection, as anode；
(3) sodium carbonate and potassium carbonate are sufficiently mixed, are placed in crucible, then crucible is placed in reactor, closed reactor is taken out Vacuum is simultaneously warming up to 450~550 DEG C, and keeps the temperature 10~15h, carries out dehydrating and removing impurities processing, the carbonate after obtaining dehydrating and removing impurities； Wherein, by molar content, sodium carbonate is 45~70mol%, and potassium carbonate is 55~30mol%；
(4) above the carbonate after cathode of composite material, foam nickel cathode, anode to be suspended in dehydrating and removing impurities, to reactor In be continually fed into argon gas so that reactor in formed argon atmosphere；
Step 3: preelectrolysis
After the fusion temperature of carbonate after reactor to be heated to dehydrating and removing impurities, fused salt is formed, reaction temperature is then heated to； By in foam nickel cathode, anode insertion fused salt, applies voltage at foam nickel cathode, anode both ends, carry out preelectrolysis, preelectrolysis knot Shu Hou takes out foam nickel cathode from fused salt；The reaction temperature is higher than the fusion temperature of the carbonate after dehydrating and removing impurities by 40 ±5℃；
Step 4: electrolysis
Cathode of composite material is inserted into fused salt and is electrolysed, applies voltage in cathode of composite material and anode both ends, carries out permanent Potential electrolysis, the cathode of composite material product after being electrolysed；Wherein, decomposition voltage be 1.8V~2.8V, electrolysis time be 1~ 12h；
Step 5: post-processing
Cathode of composite material product after electrolysis is taken out from fused salt, cooling, cleaning removal fused salt is dry, obtains coal and an oxygen Change the anode material of lithium-ion battery of manganese.
2. the preparation method of the anode material of lithium-ion battery of coal according to claim 1 and manganese monoxide, feature exist In in the step 1, preparing the composite material of coal dust and bivalent manganese source, preparation method is using one of following two:
The first: the composite material of coal dust and manganese monoxide
According to raw material proportioning in composite material, after coal dust and manganese monoxide are ground, ball milling mixing, sieves, obtain coal dust and one Average diameter < 0.1mm of the composite material of the composite material of manganese oxide, coal dust and manganese monoxide；
Second: the composite material of coal dust and manganous hydroxide
According to raw material proportioning in composite material, soluble manganous salt, consumption of oxalic acid are calculated, by coal dust, oxalic acid, soluble divalent The aqueous solution of manganese salt mixes, and obtains mixed liquor, is stirred to react to liquid internal uniformly without obvious layering, is separated by solid-liquid separation, by solid After product drying, the composite material of coal dust and manganous hydroxide is obtained, the average diameter of the composite material of coal dust and manganous hydroxide < 0.1mm。
3. the preparation method of the anode material of lithium-ion battery of coal according to claim 2 and manganese monoxide, feature exist In in the method for preparing the composite material of coal dust and bivalent manganese source；The mass concentration of the oxalic acid is 0.5~2mol/L；Institute The separation of solid and liquid stated is to carry out suction filtration separation using 0.45 μm of filter membrane when using filtering to filter or being centrifuged；The drying, Using being placed in a vacuum drying oven in 60~90 DEG C of 10~15h of drying.
4. the preparation method of the anode material of lithium-ion battery of coal according to claim 1 and manganese monoxide, feature exist In in the step 2 (1), tablet forming technique is that tableting pressure is 2~4MPa, and the dwell time is 0.5~2min.
5. the preparation method of the anode material of lithium-ion battery of coal according to claim 1 and manganese monoxide, feature exist In, in the step 2 (2), quality purity >=99.9wt.% of the nickel foam；The diameter of the iron wire be 0.3 ± 0.01mm；The diameter of the stainless steel wire collector is 2.0 ± 0.1mm；Nickel-base alloy is ambrose alloy ferroalloy.
6. the preparation method of the anode material of lithium-ion battery of coal according to claim 1 and manganese monoxide, feature exist In, in the step 2 (3), the technique of dehydrating and removing impurities processing are as follows: sodium carbonate and potassium carbonate are placed in reactor, will be reacted Device vacuumizes, and is warming up to 450~550 DEG C, is 10Pa in vacuum pressure, dry 10~15h.
7. the preparation method of the anode material of lithium-ion battery of coal according to claim 1 and manganese monoxide, feature exist In in the step 3, preelectrolysis voltage is 1.8V~2.2V, and the preelectrolysis time is 1~3h.
8. the preparation method of the anode material of lithium-ion battery of coal according to claim 1 and manganese monoxide, feature exist In in the step 4, electrolysis temperature is 30 DEG C~50 DEG C higher than fused salt fusion temperature.
9. the anode material of lithium-ion battery of a kind of coal and manganese monoxide, which is characterized in that any one using claim 1~8 Preparation method described in is made, and the anode material of lithium-ion battery of the coal of preparation and manganese monoxide is grain structure, and partial size < 100 μm, be the mixture of carbon and sub- manganese.
10. a kind of sodium-ion battery, which is characterized in that the sodium-ion battery including coal as claimed in claim 9 and manganese monoxide Negative electrode material, the sodium-ion battery coulombic efficiency of preparation is up to 98%~105%.
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