CN104979549A - Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material - Google Patents

Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material Download PDF

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CN104979549A
CN104979549A CN201510329840.7A CN201510329840A CN104979549A CN 104979549 A CN104979549 A CN 104979549A CN 201510329840 A CN201510329840 A CN 201510329840A CN 104979549 A CN104979549 A CN 104979549A
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lithium
anode material
based anode
salt
sheet
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张一笛
罗志雄
涂江平
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Hangzhou Langxin New Material Technology Co Ltd
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Hangzhou Langxin New Material Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention discloses a preparation method of a sheet lithium-enriched manganese-based anode material for a lithium-ion battery . The preparation method comprises the following steps: dissolving lithium salt, nickel salt, manganese salt and cobalt salt into ethylene glycol, and mixing and dissolving the salt to obtain a metal salt-ethylene glycol solution; drying and grinding the metal salt-ethylene glycol solution to obtain metal salt solid powder; calcining the metal salt solid powder for 3-6h at the temperature of 400-600 DEG C for the first time to obtain sheet lithium transitional metal oxide precursor powder; and fully and uniformly mixing the sheet lithium transitional metal oxide precursor powder with excessive potassium chloride, calcining the mixture for 10-30h at the temperature of 780-950 DEG C for the second time, then cooling, cleaning, and drying the mixture to obtain the sheet lithium-enriched manganese-based anode material for the lithium-ion battery . The present invention further discloses the sheet lithium-enriched manganese-based anode material for the lithium-ion battery and application of the sheet lithium-enriched manganese-based anode material for the lithium-ion battery. According to sheet lithium-enriched manganese-based anode material for the lithium-ion battery as well as the preparation method and the application of the sheet lithium-enriched manganese-based anode material for the lithium-ion battery disclosed by the present invention, relatively high cycle stability can be further kept while the rate capability of the material is improved.

Description

Lithium-rich manganese-based anode material for lithium-ion batteries of sheet and its preparation method and application
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, be specifically related to lithium-rich manganese-based anode material for lithium-ion batteries of a kind of sheet and its preparation method and application.
Background technology
Lithium ion battery is a kind of desirable novel battery, have that specific energy is high, operating voltage is high, capacity is large, have extended cycle life, self discharge is low, multiplying power discharging property good, memory-less effect, the advantage such as safe and reliable, environmental protection, compared with traditional nickel-cadmium cell, Ni-MH battery, there is obvious advantage.At present, lithium ion battery is widely used in the electronic equipments such as mobile phone, notebook computer, camera and digital camera, and will obtain deeper development and application in fields such as electric automobile, Aero-Space, national defense industry.
LiCoO 2be the anode material for lithium-ion batteries be most widely used at present, but Co scarcity of resources, price are high, poisonous and poor stability, Development of Novel positive electrode is extremely urgent.LiNi 1-x-yco xmn yo 2stratified material has the advantages such as cost is low, specific capacity is high, cyclicity is good, security performance is good, environmental protection.Wherein, manganese can reduce material cost, provides stable skeleton, improve security performance; Nickel provides the electronics required for redox reaction; Cobalt can effectively suppress " cation mixing ", improves material conductivity.But its capacity only has 200mAh/g under 2.5 ~ 4.6V.
Research finds, if lithium is suitably excessive can obtain xLi 2mnO 3(1-x) LiMO 2(M=Ni, Co, Mn) rich lithium manganese anode material, make structure more stable and can improve discharge capacity, between 2 ~ 4.8V, charge/discharge capacity can reach more than 250mAh/g, demonstrates good application prospect.But the first charge-discharge efficiency of lithium-rich manganese-based anode material for lithium-ion batteries is lower, cycle performance and high rate performance to be improved.
The conventional method preparing rich lithium manganese material mainly contains: coprecipitation, spray pyrolysis, sol-gal process, combustion method, solid reaction process etc.The pattern controlling material by different preparation methods has become the method for the lithium-rich manganese-based anode material for lithium-ion batteries performance of a kind of effective raising.Nano level rich lithium manganese anode material due to lithium ion the evolving path when carrying out electrochemical reaction shorter and there is more excellent chemical property.
Publication number is the preparation method that the Chinese invention patent application of CN 101139108A (application number is 200610113009.9) discloses a kind of laminated Li-Ni cobalt and manganese oxide anode material of lithium ion battery, specifically comprises: by the compound of the compound of manganese powder, lithium, metallic cobalt or cobalt, the compound of nickel by chemical formula Li yni xc o1-2xmn xo 2express the mol ratio required and take corresponding above-mentioned raw materials, in formula, 0 < x < 0.5,0.9 < y < 1.1; Add solvent in raw material and carry out wet-milling; Wet-milling post-drying; Sinter under high temperature, grinding obtains laminated Li-Ni cobalt and manganese oxide anode material again.Although the material specific capacity obtained is greater than 150mAh/g, tap density is greater than 2.3g/cm 3, be the tap density of Material synthesis material with manganese compound higher than conventional solid-state method, but its capacity still needs further raising.
Application publication number is the preparation method that the Chinese invention patent application of CN 103956477A (application number is 201410176821.0) discloses a kind of rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion battery plus plate material contains Li, Ni, Co, Mn and O element, and its molecular formula is Li 1.2ni 0.13c o0.13mn 0.54o 2, specifically comprise the following steps: (1), by organic precipitant water bath with thermostatic control stir be dissolved in organic solvent, obtain solution 1; (2), by the cobalt salt of solubility, nickel salt, manganese salt and lithium salts ultrasonic dissolution in deionized water, solution 2 is obtained; (3) solution 2 of gained is at the uniform velocity added drop-wise in solution 1, control temperature 100 ~ 200 DEG C oven dry, obtain pressed powder, be warming up to 200 DEG C of insulation 2 ~ 4h again, and then be warming up to 400 ~ 500 DEG C of precalcining 4 ~ 6h, then be warming up to 800 ~ 900 DEG C of precalcining 6 ~ 18h, namely obtain rich lithium ternary compound potassium ion battery plus plate material with stove cool to room temperature.Under 1C multiplying power, 100 average discharge capacity are 174.2mAh/g, and under 2C multiplying power, 100 average discharge capacity are 155.7mAh/g, and its electric property needs to be improved further.
Summary of the invention
The invention provides the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of a kind of sheet, sheet presoma is prepared as solvent with ethylene glycol, then in potassium chloride fuse salt environment, high-temperature heat treatment obtains nano lamellar material, and technique is simple, cost is low, product uniformity is good.
A preparation method for the lithium-rich manganese-based anode material for lithium-ion batteries of sheet, comprises the following steps:
1) lithium salts, nickel salt, manganese salt and cobalt salt are dissolved in ethylene glycol, mixed dissolution, obtain slaine ethylene glycol solution;
2) slaine ethylene glycol solution dried and grind, obtaining metal salt solid powder;
3) metal salt solid powder first time at 400 DEG C ~ 600 DEG C is calcined 3h ~ 6h, obtain flaky lithium transition metal oxide precursor body powder;
4) fully mixed with excess chlorination potassium by flaky lithium transition metal oxide precursor body powder, at 780 DEG C ~ 950 DEG C, second time calcines 10h ~ 30h, cools afterwards, after cleaning, drying, obtains the lithium-rich manganese-based anode material for lithium-ion batteries of sheet.
In the present invention, sheet presoma is prepared as solvent with ethylene glycol, solvent is not only by ethylene glycol, simultaneously also as chelate stabilizer, crystal can be made to form nanometer sheet perpendicular to a direction growth, then in potassium chloride fuse salt environment, high-temperature heat treatment obtains nano lamellar material, in potassium chloride melting Ficus caricaL process, and the K of positively charged +be combined in the surface of lithium transition-metal oxide, because its volume is comparatively large, hindered crystal growth in a certain direction, thus obtain platelet morphology, the inventive method technique is simple, cost is low, product uniformity has been good.
Step 1) in, the amount of lithium salts, nickel salt, manganese salt and cobalt salt mainly adds by the stoichiometric proportion of lithium corresponding in required lithium-rich manganese-based anode material for lithium-ion batteries, nickel, manganese, each element of cobalt, general lithium salts wants excessive 1% ~ 6%, thus offsets the loss of lithium under high temperature.As preferably, described lithium salts is LiNO 3, LiCH 3cOO2H 2o or both mixtures.Described nickel salt is Ni (NO 3) 26H 2o, Ni (CH 3cOO) 24H 2o or both mixtures.Described manganese salt is Mn (NO 3) 24H 2o, Mn (CH 3cOO) 24H 2o or both mixtures.Described cobalt salt is Co (NO 3) 26H 2o, Co (CH 3cOO) 24H 2o or both mixtures.The lithium salts of above-mentioned selection, nickel salt, manganese salt and cobalt salt complete reaction can generate a large amount of gas in high-temperature heat treatment process, make other anion residual in the lithium transition-metal oxide obtained.
As preferably, in described slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.1mol/L ~ 0.5mol/L, above-mentioned concentration metal salt ethylene glycol solution can ensure the abundant dissolving of lithium salts, nickel salt, manganese salt and cobalt salt, and solvent is not only by ethylene glycol, simultaneously also as chelate stabilizer, crystal can be made to form nanometer sheet perpendicular to a direction growth.Further preferably, in described slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.2mol/L ~ 0.4mol/L.
As preferably, the condition of described mixed dissolution is: magnetic agitation 2h ~ 12h in 50 DEG C ~ 90 DEG C water bath, can ensure that slaine dissolves completely and stirs.Further preferably, the condition of described mixed dissolution is: magnetic agitation 6h ~ 10h in 70 DEG C ~ 85 DEG C water bath.
Step 2) in, as preferably, bake out temperature is 120 DEG C ~ 200 DEG C.The boiling point of ethylene glycol is 197.3 DEG C, and further preferably, bake out temperature is 180 DEG C ~ 200 DEG C, is conducive to ethylene glycol rapid evaporation, and can not acutely seethe with excitement causes solution to splash simultaneously.
Step 3) in, metal salt solid powder first time at 400 DEG C ~ 600 DEG C is calcined 3h ~ 6h, and calcination process carries out in atmosphere, and heating rate is 2 ~ 20 DEG C/min, is conducive to removing most ethylene glycol, nitrate anion and acetate.Further preferably, metal salt solid powder first time at 400 DEG C ~ 500 DEG C is calcined 3h ~ 6h, heats up with 2 ~ 5 DEG C/min, be conducive to forming sheet lithium transition-metal oxide presoma.
Step 4) in, as preferably, described flaky lithium transition metal oxide precursor body powder and the mass ratio of potassium chloride are 1:4 ~ 1:8.In potassium chloride melting Ficus caricaL process, the K of positively charged +be combined in the surface of lithium transition-metal oxide, because its volume is comparatively large, has hindered crystal growth in a certain direction, thus obtain platelet morphology.Under this ratio, ensure that on the one hand potassium chloride is fully excessive, can submergence lithium transition-metal oxide precursor powder after melting, make potassium chloride can not be too much on the other hand, be conducive to sintered after the potassium chloride in product is washed off completely.
At 780 DEG C ~ 950 DEG C, second time calcines 10h ~ 30h, and calcination process carries out in atmosphere, and heating rate is 2 ~ 20 DEG C/min.After preliminary heat treatment, basically formed the thing phase of positive electrode, but due to the reaction time short, temperature is not high, and the layer structure of material and crystallinity are not good.In order to improve material crystalline further, improving the layer structure of material, forming sheet-like morphology, remove simultaneously wherein may remaining under organic principle, thus carry out high-temperature calcination.As preferably, at 800 DEG C ~ 900 DEG C, calcine 12h ~ 24h for the second time, heat up with 5 ~ 10 DEG C/min, be conducive to the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of the crystallinity excellence obtained.
Described cooling refers to and is cooled to temperature 20 ~ 40 DEG C, is generally cooled to ambient temperature.
Present invention also offers the lithium-rich manganese-based anode material for lithium-ion batteries of a kind of sheet, be the ternary layered structure oxide of the rich lithium of one, there is uniform nano-sheet pattern, and have good crystallinity.Obtain the lithium-rich manganese-based anode material for lithium-ion batteries of sheet that conventional method is difficult to prepare, nanometer thin sheet-like morphology can effectively shorten lithium ion the evolving path, while raising material high rate performance, can keep higher cyclical stability again.
The lithium-rich manganese-based anode material for lithium-ion batteries of described sheet, its chemical formula is Li [Li xmn yni zco 1-x-y-z] O 2, 0.1≤x≤0.3,0.46≤y≤0.66,0.06≤z≤0.26.As preferably, be Li [Li 0.2mn 0.56ni 0.16co 0.08] O 2, or, be Li [Li 0.2mn 0.54ni 0.13co 0.13] O 2.
Manganese element is+4 valencys, plays the effect of charge compensation; Nickel is+divalent, is main redox reaction active material, provides most of capacity; Cobalt is+3 valencys, and cobalt, being charged under high voltage and redox reaction can occurring, provides fraction capacity, in addition, is conducive to the adding of cobalt the mixing reducing lithium nickel ion, improves the structure of material, improve the order of Atomic Arrangement.
Present invention also offers the application of the lithium-rich manganese-based anode material for lithium-ion batteries of a kind of sheet, lithium-rich manganese-based for sheet anode material for lithium-ion batteries is prepared lithium ion cell positive, then lithium ion cell positive is applied in lithium ion battery, reversible capacity is high, stable cycle performance and there is good rate charge-discharge performance.
A kind of lithium ion cell positive, comprises the following steps:
Lithium-rich manganese-based for sheet anode material for lithium-ion batteries is mixed 1:0.02 ~ 0.1:0.02 ~ 0.1 in mass ratio with adhesive polyvinylidene fluoride (PVDF) and conductive carbon black, add appropriate 1-methyl 2-Pyrrolidone and stir into pasty state, evenly be coated in aluminium foil surface, then at 90 DEG C, 12h is dried, repressed shaping after, be placed in vacuum drying oven again in 90 DEG C of dry 12h, lithium ion cell positive is made in section.
Lithium ion cell positive and lithium ion battery negative (metal lithium sheet) are assembled into lithium ion battery.Lithium ion battery adopts microporous polypropylene membrane (Cellgard 2300) to be barrier film, using the diethyl carbonate of volume ratio 7:3 (DEC) and ethylene carbonate (EC) as solvent, by LiPF 6be dissolved in solvent, obtained electrolyte, LiPF in electrolyte 6concentration be 1mol/L.Lithium ion battery assembling process completes in water volume content is lower than the dry glove box of 0.1ppm.The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, and charging/discharging voltage is 2.0V ~ 4.8V, and circulate Reversible lithium insertion capacity, charge-discharge performance and the multiplying power property of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
Compared with prior art, tool of the present invention has the following advantages:
The preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of the present invention, compared with traditional coprecipitation, without the need to accurately controlling the temperature, pH value, charging rate etc. of co-precipitation system, technique simply, easily operates.And obtain the lithium-rich manganese-based anode material for lithium-ion batteries of sheet that conventional method is difficult to prepare, nanometer thin sheet-like morphology can effectively shorten lithium ion the evolving path, while raising material high rate performance, higher cyclical stability can be kept again.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by embodiment 1;
Fig. 2 is the stereoscan photograph of flaky lithium transition metal oxide precursor body powder prepared by embodiment 1;
Fig. 3 is the stereoscan photograph of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by embodiment 1.
Embodiment
Embodiment 1
1) by the mol ratio of 1.236:0.56:0.16:0.08 by raw material LiNO 3, Mn (CH 3cOO) 24H 2o, Ni (NO 3) 26H 2o and Co (NO 3) 26H 2o is dissolved in ethylene glycol (wherein adding the lithium salts of excessive 3%, for offsetting the loss of lithium under high temperature), and form slaine ethylene glycol solution, in slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.26mol/L.Magnetic agitation 8h in 85 DEG C of water bath, obtains the slaine ethylene glycol solution of claret.
2) the slaine ethylene glycol solution of claret is placed in 200 DEG C of baking ovens dry and grind, obtains metal salt solid powder;
3) be that 2 DEG C/min is warming up to 450 DEG C by metal salt solid powder with heating rate, at 450 DEG C, calcine 5h, heating rate is 2 DEG C/min, obtains flaky lithium transition metal oxide precursor body powder;
4) flaky lithium transition metal oxide precursor body powder is fully mixed with the ratio of mass ratio 1:5 with potassium chloride, be warming up to 800 DEG C with 5 DEG C/min, calcining 12h, is cooled to room temperature 25 DEG C, after washed with de-ionized water, oven dry, obtain the lithium-rich manganese-based anode material for lithium-ion batteries of sheet.
By the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of preparation by X-ray diffraction (X-raydiffraction) test.As shown in Figure 1, be the lithium-rich manganese-based anode material for lithium-ion batteries Li of sheet [Li prepared by the present embodiment 0.2mn 0.56ni 0.16co 0.08] O 2x-ray diffractogram.As can be seen from the X-ray diffractogram of Fig. 1, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared of the present embodiment except the superlattice diffraction maximum (020) between 20 ° ~ 25 ° and ( ) beyond, all corresponding stratiform α-NaFeO of other diffraction maximums 2structure, belongs to hexagonal crystal system, space group.Satellites between 20 ° ~ 25 ° shows Li 2mnO 3the existence of ordered structure microcell, this microcell is also layer structure, belongs to C/2m space group.(006)/(012) of obvious division and (018)/(110) peak interpret sample good crystallinity and define layer structure.As can be seen from Figure 2, flaky lithium transition metal oxide precursor body powder prepared by the present embodiment is equally distributed nano flake, and thickness is at below 10nm.As can be seen from Figure 3, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by the present embodiment is equally distributed nanometer sheet, and thickness has increase to a certain degree compared with presoma, is 30 ~ 50nm.After testing, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of the present invention is Li [Li 0.2mn 0.56ni 0.16co 0.08] O 2.
By the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of preparation and adhesive polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd., model is FR901) and conductive carbon black 90:5:5 mixing in mass ratio, obtain compound, add 1-methyl 2-Pyrrolidone (NMP again, add by compound and 1-methyl 2-Pyrrolidone volume ratio 1:1) stir into pasty state, evenly be coated in aluminium foil surface, then at 90 DEG C, 12h is dried, after roll squeezer is compressing, be placed in vacuum drying oven again in 90 DEG C of dry 12h, lithium ion cell positive is made in section.
The lithium ion cell positive of preparation and lithium ion battery negative (metal lithium sheet) are assembled into lithium ion battery.Lithium ion battery adopts microporous polypropylene membrane (Cellgard 2300) to be barrier film, using the diethyl carbonate of volume ratio 7:3 (DEC) and ethylene carbonate (EC) as solvent, by LiPF 6be dissolved in solvent, obtained electrolyte, LiPF in electrolyte 6concentration be 1mol/L.Lithium ion battery assembling process completes in water volume content is lower than the dry glove box of 0.1ppm.The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, and charging/discharging voltage is 2.0V ~ 4.8V, and circulate Reversible lithium insertion capacity, charge-discharge performance and the high-rate characteristics of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
After being assembled into lithium ion battery, lithium ion battery has the discharge capacity first of 274mAh/g under current density 20mA/g, and after 30 circulations, discharge capacity maintains 243.3mAh/g.As shown in table 1, reach 196.4mAh/g and 125.1mAh/g at current density 200mA/g and 1000mA/g discharge capacity.After current density 200mA/g discharge and recharge 50 circulation, reversible charge/discharge capacity remains on 192.6mAh/g, and capability retention is up to 98%.Visible above-mentioned capacity of lithium ion battery is high, good cycling stability.
Embodiment 2
1) by the mol ratio of 1.236:0.54:0.13:0.13 by raw material LiNO 3, Mn (CH 3cOO) 24H 2o, Ni (NO 3) 26H 2o and Co (NO 3) 26H 2o is dissolved in ethylene glycol (wherein adding the lithium salts of excessive 3%, for offsetting the loss of lithium under high temperature), and form slaine ethylene glycol solution, in slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.3mol/L.Magnetic agitation 8h in 85 DEG C of water bath, obtains the slaine ethylene glycol solution of claret.
2) the slaine ethylene glycol solution of claret is placed in 200 DEG C of baking ovens dry and grind, obtains metal salt solid powder;
3) metal salt solid powder is calcined 5h at 450 DEG C, heating rate is 2 DEG C/min, obtains flaky lithium transition metal oxide precursor body powder;
4) lithium transition-metal oxide precursor powder is fully mixed with the ratio of mass ratio 1:5 with potassium chloride, be warming up to 900 DEG C with 5 DEG C/min, calcining 12h, is cooled to room temperature 25 DEG C, after washed with de-ionized water, oven dry, obtain the lithium-rich manganese-based anode material for lithium-ion batteries of sheet.
As can be seen from X-ray diffractogram, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared of the present embodiment except the superlattice diffraction maximum (020) between 20 ° ~ 25 ° and ( ) beyond, all corresponding stratiform α-NaFeO of other diffraction maximums 2structure, belongs to hexagonal crystal system, space group.Satellites between 20 ° ~ 25 ° shows Li 2mnO 3the existence of ordered structure microcell, this microcell is also layer structure, belongs to C/2m space group.(006)/(012) of obvious division and (018)/(110) peak interpret sample good crystallinity and define layer structure.From the stereoscan photograph of flaky lithium transition metal oxide precursor body powder, flaky lithium transition metal oxide precursor body prepared by the present embodiment is equally distributed nano flake, and thickness is at below 10nm.From the stereoscan photograph of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by the present embodiment is equally distributed nanometer sheet, and thickness has increase to a certain degree compared with presoma, is 30 ~ 50nm.After testing, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of the present invention is Li [Li 0.2mn 0.54ni 0.13co 0.13] O 2.
By the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of preparation and adhesive polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd., model is FR901) and conductive carbon black 90:5:5 mixing in mass ratio, obtain compound, add 1-methyl 2-Pyrrolidone (NMP again, add by compound and 1-methyl 2-Pyrrolidone volume ratio 1:1) stir into pasty state, evenly be coated in aluminium foil surface, then at 90 DEG C, 12h is dried, after roll squeezer is compressing, be placed in vacuum drying oven again in 90 DEG C of dry 12h, lithium ion cell positive is made in section.
The lithium ion cell positive of preparation and lithium ion battery negative (metal lithium sheet) are assembled into lithium ion battery.Lithium ion battery adopts microporous polypropylene membrane (Cellgard 2300) to be barrier film, using the diethyl carbonate of volume ratio 7:3 (DEC) and ethylene carbonate (EC) as solvent, by LiPF 6be dissolved in solvent, obtained electrolyte, LiPF in electrolyte 6concentration be 1mol/L.Lithium ion battery assembling process completes in water volume content is lower than the dry glove box of 0.1ppm.The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, and charging/discharging voltage is 2.0V ~ 4.8V, and circulate Reversible lithium insertion capacity, charge-discharge performance and the high-rate characteristics of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
After being assembled into lithium ion battery, lithium ion battery has the discharge capacity first of 278.4mAh/g under current density 20mA/g, and after 30 circulations, discharge capacity maintains 250.2mAh/g.As shown in table 1, reach 192.8mAh/g and 115.3mAh/g at current density 200mA/g and 1000mA/g discharge capacity.After current density 200mA/g discharge and recharge 50 circulation, reversible charge/discharge capacity remains on 189.7mAh/g.
Embodiment 3
1) by the mol ratio of 1.236:0.56:0.16:0.08 by raw material LiNO 3, Mn (CH 3cOO) 24H 2o, Ni (NO 3) 26H 2o and Co (NO 3) 26H 2o is dissolved in ethylene glycol (wherein adding the lithium salts of excessive 3%, for offsetting the loss of lithium under high temperature), and form slaine ethylene glycol solution, in slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.3mol/L.Magnetic agitation 8h in 80 DEG C of water bath, obtains the slaine ethylene glycol solution of claret.
2) the slaine ethylene glycol solution of claret is placed in 200 DEG C of baking ovens dry and grind, obtains metal salt solid powder;
3) metal salt solid powder is calcined 5h at 500 DEG C, heating rate is 2 DEG C/min, obtains flaky lithium transition metal oxide precursor body powder;
4) lithium transition-metal oxide precursor powder is fully mixed with the ratio of mass ratio 1:4 with potassium chloride, be warming up to 850 DEG C with 5 DEG C/min, calcining 16h, is cooled to room temperature 25 DEG C, after washed with de-ionized water, oven dry, obtain the lithium-rich manganese-based anode material for lithium-ion batteries of sheet.
As can be seen from X-ray diffractogram, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared of the present embodiment except the superlattice diffraction maximum (020) between 20 ° ~ 25 ° and ( ) beyond, all corresponding stratiform α-NaFeO of other diffraction maximums 2structure, belongs to hexagonal crystal system, space group.Satellites between 20 ° ~ 25 ° shows Li 2mnO 3the existence of ordered structure microcell, this microcell is also layer structure, belongs to C/2m space group.(006)/(012) of obvious division and (018)/(110) peak interpret sample good crystallinity and define layer structure.From the stereoscan photograph of flaky lithium transition metal oxide precursor body powder, flaky lithium transition metal oxide precursor body prepared by the present embodiment is equally distributed nano flake, and thickness is at below 10nm.From the stereoscan photograph of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by the present embodiment is equally distributed nanometer sheet, and thickness has increase to a certain degree compared with presoma, is 40 ~ 60nm.After testing, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of the present invention is Li [Li 0.2mn 0.56ni 0.16co 0.08] O 2.
By the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of preparation and adhesive polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd., model is FR901) and conductive carbon black 90:5:5 mixing in mass ratio, obtain compound, add 1-methyl 2-Pyrrolidone (NMP again, add by compound and 1-methyl 2-Pyrrolidone volume ratio 1:1) stir into pasty state, evenly be coated in aluminium foil surface, then at 90 DEG C, 12h is dried, after roll squeezer is compressing, be placed in vacuum drying oven again in 90 DEG C of dry 12h, lithium ion cell positive is made in section.
The lithium ion cell positive of preparation and lithium ion battery negative (metal lithium sheet) are assembled into lithium ion battery.Lithium ion battery adopts microporous polypropylene membrane (Cellgard 2300) to be barrier film, using the diethyl carbonate of volume ratio 7:3 (DEC) and ethylene carbonate (EC) as solvent, by LiPF 6be dissolved in solvent, obtained electrolyte, LiPF in electrolyte 6concentration be 1mol/L.Lithium ion battery assembling process completes in water volume content is lower than the dry glove box of 0.1ppm.The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, and charging/discharging voltage is 2.0V ~ 4.8V, and circulate Reversible lithium insertion capacity, charge-discharge performance and the high-rate characteristics of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
After being assembled into lithium ion battery, lithium ion battery has the discharge capacity first of 286.7mAh/g under current density 20mA/g, and after 30 circulations, discharge capacity maintains 254.6mAh/g.As shown in table 1, reach 206.8mAh/g and 131.2mAh/g at current density 200mA/g and 1000mA/g discharge capacity.After current density 200mA/g discharge and recharge 50 circulation, reversible charge/discharge capacity remains on 202.1mAh/g.
Embodiment 4
1) by the mol ratio of 1.236:0.54:0.13:0.13 by raw material LiNO 3, Mn (CH 3cOO) 24H 2o, Ni (CH 3cOO) 24H 2o and Co (CH 3cOO) 24H 2o is dissolved in ethylene glycol (wherein adding the lithium salts of excessive 3%, for offsetting the loss of lithium under high temperature), and form slaine ethylene glycol solution, in slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.4mol/L.Magnetic agitation 10h in 80 DEG C of water bath, obtains the slaine ethylene glycol solution of claret.
2) the slaine ethylene glycol solution of claret is placed in 200 DEG C of baking ovens dry and grind, obtains metal salt solid powder;
3) metal salt solid powder is calcined 5h at 450 DEG C, heating rate is 2 DEG C/min, obtains flaky lithium transition metal oxide precursor body powder;
4) lithium transition-metal oxide precursor powder is fully mixed with the ratio of mass ratio 1:6 with potassium chloride, be warming up to 800 DEG C with 5 DEG C/min, calcining 20h, is cooled to room temperature 25 DEG C, after washed with de-ionized water, oven dry, obtain the lithium-rich manganese-based anode material for lithium-ion batteries of sheet.
As can be seen from X-ray diffractogram, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared of the present embodiment except the superlattice diffraction maximum (020) between 20 ° ~ 25 ° and ( ) beyond, all corresponding stratiform α-NaFeO of other diffraction maximums 2structure, belongs to hexagonal crystal system, space group.Satellites between 20 ° ~ 25 ° shows Li 2mnO 3the existence of ordered structure microcell, this microcell is also layer structure, belongs to C/2m space group.(006)/(012) of obvious division and (018)/(110) peak interpret sample good crystallinity and define layer structure.From the stereoscan photograph of flaky lithium transition metal oxide precursor body powder, flaky lithium transition metal oxide precursor body prepared by the present embodiment is equally distributed nano flake, and thickness is at below 10nm.From the stereoscan photograph of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by the present embodiment is equally distributed nanometer sheet, and thickness has increase to a certain degree compared with presoma, is 40 ~ 60nm.After testing, the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of the present invention is Li [Li 0.2mn 0.54ni 0.13co 0.13] O 2.
By the lithium-rich manganese-based anode material for lithium-ion batteries of sheet of preparation and adhesive polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd., model is FR901) and conductive carbon black 90:5:5 mixing in mass ratio, obtain compound, add 1-methyl 2-Pyrrolidone (NMP again, add by compound and 1-methyl 2-Pyrrolidone volume ratio 1:1) stir into pasty state, evenly be coated in aluminium foil surface, then at 90 DEG C, 12h is dried, after roll squeezer is compressing, be placed in vacuum drying oven again in 90 DEG C of dry 12h, lithium ion cell positive is made in section.
The lithium ion cell positive of preparation and lithium ion battery negative (metal lithium sheet) are assembled into lithium ion battery.Lithium ion battery adopts microporous polypropylene membrane (Cellgard 2300) to be barrier film, using the diethyl carbonate of volume ratio 7:3 (DEC) and ethylene carbonate (EC) as solvent, by LiPF 6be dissolved in solvent, obtained electrolyte, LiPF in electrolyte 6concentration be 1mol/L.Lithium ion battery assembling process completes in water volume content is lower than the dry glove box of 0.1ppm.The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, and charging/discharging voltage is 2.0V ~ 4.8V, and circulate Reversible lithium insertion capacity, charge-discharge performance and the high-rate characteristics of measuring lithium ion cell positive in 25 ± 2 DEG C of environment.
After being assembled into lithium ion battery, lithium ion battery has the discharge capacity first of 270.3mAh/g under current density 20mA/g, and after 30 circulations, discharge capacity maintains 249.5mAh/g.As shown in table 1, reach 185.4mAh/g and 110.7mAh/g at current density 200mA/g and 1000mA/g discharge capacity.After current density 200mA/g discharge and recharge 50 circulation, reversible charge/discharge capacity remains on 178.6mAh/g.
The lithium-rich manganese-based anode material for lithium-ion batteries of sheet in embodiment 1 ~ 4 is prepared into lithium ion cell positive, and after being assembled into lithium ion battery, its maximum discharge capacity under the current density that do not coexist is as shown in table 1.
Table 1

Claims (10)

1. a preparation method for the lithium-rich manganese-based anode material for lithium-ion batteries of sheet, is characterized in that, comprise the following steps:
1) lithium salts, nickel salt, manganese salt and cobalt salt are dissolved in ethylene glycol, mixed dissolution, obtain slaine ethylene glycol solution;
2) slaine ethylene glycol solution dried and grind, obtaining metal salt solid powder;
3) metal salt solid powder first time at 400 DEG C ~ 600 DEG C is calcined 3h ~ 6h, obtain flaky lithium transition metal oxide precursor body powder;
4) fully mixed with excess chlorination potassium by flaky lithium transition metal oxide precursor body powder, at 780 DEG C ~ 950 DEG C, second time calcines 10h ~ 30h, cools afterwards, after cleaning, drying, obtains the lithium-rich manganese-based anode material for lithium-ion batteries of sheet.
2. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 1, is characterized in that, step 1) in, described lithium salts is LiNO 3, LiCH 3cOO2H 2o or both mixtures;
Described nickel salt is Ni (NO 3) 26H 2o, Ni (CH 3cOO) 24H 2o or both mixtures;
Described manganese salt is Mn (NO 3) 24H 2o, Mn (CH 3cOO) 24H 2o or both mixtures;
Described cobalt salt is Co (NO 3) 26H 2o, Co (CH 3cOO) 24H 2o or both mixtures.
3. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 1, it is characterized in that, step 1) in, in described slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.1mol/L ~ 0.5mol/L;
The condition of described mixed dissolution is: magnetic agitation 2h ~ 12h in 50 DEG C ~ 90 DEG C water bath.
4. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 3, it is characterized in that, step 1) in, in described slaine ethylene glycol solution, the total concentration of lithium salts, nickel salt, manganese salt and cobalt salt is 0.2mol/L ~ 0.4mol/L;
The condition of described mixed dissolution is: magnetic agitation 6h ~ 10h in 70 DEG C ~ 85 DEG C water bath.
5. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 1, is characterized in that, step 2) in, bake out temperature is 120 DEG C ~ 200 DEG C.
6. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 5, is characterized in that, step 2) in, bake out temperature is 180 DEG C ~ 200 DEG C.
7. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 1, is characterized in that, step 3) in, metal salt solid powder first time at 400 DEG C ~ 500 DEG C is calcined 3h ~ 6h, heats up with 2 ~ 5 DEG C/min;
Step 4) in, at 800 DEG C ~ 900 DEG C, second time calcines 12h ~ 24h, heats up with 5 ~ 10 DEG C/min.
8. the preparation method of the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 1, is characterized in that, step 4) in, described flaky lithium transition metal oxide precursor body powder and the mass ratio of potassium chloride are 1:4 ~ 1:8.
9. the lithium-rich manganese-based anode material for lithium-ion batteries of sheet prepared by the preparation method according to any one of claim 1 ~ 8, is characterized in that, its chemical formula is Li [Li xmn yni zco 1-x-y-z] O 2, 0.1≤x≤0.3,0.46≤y≤0.66,0.06≤z≤0.26.
10. the lithium-rich manganese-based anode material for lithium-ion batteries of sheet according to claim 9 is preparing the application in lithium ion cell positive.
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CN106935846A (en) * 2016-12-30 2017-07-07 惠州龙为科技有限公司 A kind of preparation method of the modified nickel lithium manganate cathode material of high voltage
WO2018121102A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing high-voltage modified lithium nickel manganese oxide anode material
CN108264098A (en) * 2018-02-26 2018-07-10 重庆大学 The preparation method of two-dimensional sheet lithium nickel cobalt manganese oxygen
CN108264098B (en) * 2018-02-26 2019-10-25 重庆大学 The preparation method of two-dimensional sheet lithium nickel cobalt manganese oxygen
CN108598463A (en) * 2018-02-28 2018-09-28 中国电力科学研究院有限公司 A kind of preparation method of nano-sheet lithium-rich manganese-based anode material
CN108598463B (en) * 2018-02-28 2020-11-17 中国电力科学研究院有限公司 Preparation method of nano flaky lithium-rich manganese-based positive electrode material
CN110010886A (en) * 2019-04-09 2019-07-12 上海卡耐新能源有限公司 A kind of lithium-rich manganese-based anode material, preparation method, anode pole piece and lithium ion secondary battery
CN111082044A (en) * 2019-12-19 2020-04-28 南京大学 Yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material and preparation method thereof, and lithium ion battery
CN114497452A (en) * 2021-12-28 2022-05-13 高点(深圳)科技有限公司 Positive electrode material for silicon battery and preparation method and application thereof
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