CN104795546A - Preparation method for rich lithium manganese layered solid solution and rich lithium manganese layered solid solution prepared by adopting preparation method - Google Patents

Preparation method for rich lithium manganese layered solid solution and rich lithium manganese layered solid solution prepared by adopting preparation method Download PDF

Info

Publication number
CN104795546A
CN104795546A CN201510176568.3A CN201510176568A CN104795546A CN 104795546 A CN104795546 A CN 104795546A CN 201510176568 A CN201510176568 A CN 201510176568A CN 104795546 A CN104795546 A CN 104795546A
Authority
CN
China
Prior art keywords
lithium
source
preparation
rich manganese
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510176568.3A
Other languages
Chinese (zh)
Inventor
李河杉
刘剑洪
钟登海
胡超
廖楚宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201510176568.3A priority Critical patent/CN104795546A/en
Publication of CN104795546A publication Critical patent/CN104795546A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M2004/028—Positive 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

The invention provides a preparation method for a rich lithium manganese layered solid solution and a rich lithium manganese layered solid solution prepared by adopting the preparation method. The preparation method for the rich lithium manganese layered solid solution comprises the following steps: A, performing mixed dispersion on a lithium source, a manganese source and a nickel source in a solvent, so as to obtain an uniform mixed liquid; B, performing spray drying on the mixed liquid, so as to obtain a precursor; C, preburning the precursor for 2-15h at the temperature of 100-550 DEG C under the air atmosphere, so as to obtain a preburned product; D, calcining the preburned product obtained in the step C for 5-20h at the temperature of 500-1100 DEG C under the air atmosphere, so as to obtain the rich lithium manganese layered solid solution which is (1-2y)[xLi2MnO3.(1-x)LiNi0.5Mn0.5O2].yLiNi(1-x)Mn(1+x)O4, wherein the x is greater than 0 and smaller than 1, and the y is greater than or equal to 0 and smaller than 1; the actual lithium input amount of the lithium source is 50-200% of the lithium content in the designed molecular formula. The technology used in the preparation method is creative and unique and suitable for large-scale industrial production, and the material has excellent electrochemical performance.

Description

The preparation method of lithium-rich manganese-based layed solid-solution and the lithium-rich manganese-based layed solid-solution of preparation thereof
Technical field
The present invention relates to field of lithium ion battery, be specifically related to a kind of positive electrode active materials of lithium ion battery, relate to a kind of preparation method of lithium-rich manganese-based layed solid-solution and the lithium-rich manganese-based layed solid-solution of preparation thereof more specifically.
Background technology
The development of the mankind invariably accompanies the innovation of various new technology and the application of new forms of energy, as universal along with steam engine of the first time industrial revolution; Second industrial revolution is then the application of electric power.Society, the fossil fuels such as oil, natural gas, coal are widely used, and had more than two one-hundred-year histories, the thing followed is rise in price and the energy crisis of fossil fuel.Various fossil fuel is non-renewable energy resources in addition, and reserves are extremely limited.And also to the various toxic gas of airborne release and dust while the combusts fossil energy, the acid rain caused, haze, greenhouse effect etc. have had a strong impact on life and the health of people.In addition, the energetic of electronic product and portability, as the universal of the electronic product such as laptop computer and mobile phone is also badly in need of a kind of high-energy-density and light energy source.Various reasons forces people to start to be conceived to the exploitation of new new cleaning fuel and new energy storage device.This also creates showing one's talent of lithium ion battery.
Relative to other secondary cell, the portability of lithium ion battery and high-energy-density made it in the past twenty years in led portable battery market.Now, the power resources of lithium ion battery as hybrid vehicles, the plug-in hybrid vehicles and electric vehicle are being put forth effort in the research of lithium ion battery, and lithium ion battery technology has been considered to the secondary regenerative resource that can compare favourably with wind energy, tidal energy.Lithium ion battery technology large-scale application compares in those project relying on low cost, high security, high cycle life, discharge and recharge ratio and the high-energy-density energy, and lithium ion battery technology itself also quite relies on the performance of battery material.Although scientific workers have dropped into a large amount of energy and times at the positive and negative pole material of lithium ion battery, a small amount of scientific research crystallization has wherein been only had really to achieve suitability for industrialized production.
Positive electrode is as the main carriers of lithium ion, it is the most critical material of lithium ion battery, it occupies 40% of whole lithium ion battery cost, but decide every critical performance parameters of whole lithium ion battery, as charging/discharging voltage, circulating and reversible capacity, cycle performance, fail safe, stability etc.And lithium metal oxide (LMO) be people's early start is also simultaneously study the widest lithium ion battery positive electrode.At present, the cobalt acid lithium (LiCoO of stratiform wherein 2), nickel-cobalt-manganese ternary material (LiNi 1/3co 1/3mn 1/3o 2), the LiFePO 4 (LiFePO of olivine-type 4) and spinelle shape LiMn2O4 (LiMn 2o 4) etc. commercialization.To these materials, they have following common feature: (1) has more stable physics and chemistry state; (2) lithium ion can embed fast in the material embedding go out; (3) good conduction, leads ionic; (4) higher specific capacity is possessed, (5) high voltage and higher energy density; (6) in charge and discharge process, nothing or less side reaction occur, and Stability Analysis of Structures even also has certain anti-over-charging ability; (7) can carry out with lithium that reversible embedding is embedding to go out to react; (8) cost is lower, environmental pollution is less, and safer.
The more lithium metal oxide positive electrode of current research has the acid of stratiform cobalt lithium, LiMn2O4, nickel-cobalt-manganese ternary material, spinel lithium manganate, olivine-type LiFePO 4 material etc.These lithium metal oxide materials have respective pluses and minuses, as:
Cobalt acid lithium is typical layer structure, there is excellent cyclical stability and high rate performance, its theoretical capacity is up to 274mAh/g, but in reality test uses, find that the actual available specific discharge capacity of lithium cobaltate cathode material only has about 140mAh/g (about theoretical capacity 50%), and research in recent years thiss is presumably because when lithium ion is from LiCoO 2middle deintercalation forms Li 1-xcoO 2, and work as 50%Li +after deviating from from interlayer, namely as x=0.5, layer structure is easily caved in, crystal structure easily changes, thus causes the loss of reversible capacity, and the fracture of Co-O likely occurs in addition, the fail safe of battery is reduced greatly, even blast, the limit that therefore can only control to react by reducing the charging/discharging voltage upper limit (4.2V, vs.C) at present avoids layer structure to change.In addition, the cost of Co is very high and have severe toxicity, and these various reasons also all mean that cobalt acid lithium cannot become desirable anode material for lithium-ion batteries.
LiFePO4 is typical olivine-type structure, but it often has to pass through the modifications such as coated, doping, and especially carbon coated, just can have following characteristics: high high-temp stability is good, and self-discharge phenomenon is not obvious; Source material is cheap and easy to get simultaneously, safety non-toxic; Add stable charge and discharge platform, excellent cycle performance and high rate performance.But it still has some obvious shortcomings: its charge and discharge platform lower (≈ 3.5V), theoretical capacity is 170mAh/g, and actual capacity is also the highest can only accomplish about 155mAh/g, and this is relative to other positive electrodes or relatively low.
Spinel lithium manganate is typical spinel structure, its synthesis needed raw material manganese system aboundresources, cheap, nontoxic, and synthesis technique is fairly simple, and stability of material is fine.But because its theoretical specific capacity is only 147.8mAh/g, and Mn is a kind of existence of compound valence state+3.5, its lattice in hot conditions and battery charge and discharge process easily destroys, specific capacity and cycle performance degradation, this is mainly caused by following three large reasons: (1) Jahn-Teller effect; (2) Mn 2+melting; (3) decomposition of electrolyte.Just because of all more serious shortcomings above, it also cannot become separately desirable anode material for lithium-ion batteries.
And lithium metal oxide is as most widely used anode material for lithium-ion batteries, in order to overcome the specific limitation of homogenous material, (specific capacity of cyclical stability, good rate capability is low; The cyclical stability that specific capacity is high, high rate performance are bad), it is the focus that researchers study that scheme that is coated to it, doping vario-property becomes, and the common and nickel-cobalt-manganese ternary composite material be commercially used is exactly an exemplary.
Nickel-cobalt-manganese ternary composite material is also layer structure, and in material, Ni is+divalent in theory, and Co is+3 valencys, and Mn is+4 valencys, is all the valence state that respective chemical property is more stable respectively.Its theoretical capacity is up to 285mAh/g, and it solves the difficulty of pure lithium nickelate synthesis on the one hand; Decrease the consumption of cobalt on the other hand, reduce cost, improve the fail safe of material, also improve discharge and recharge limit compared to cobalt acid lithium simultaneously; And the Mn of pure+4 valencys problems such as to solve former layered lithium manganate thermal stability very poor, and structure is variable.LiNi can be said 1/3co 1/3mn 1/3o 2the cyclical stability, the high rate performance that combine stratiform cobalt acid lithium, the comprehensive embodiment of the high voltage capability of stratiform lithium nickelate and the non-toxic inexpensive characteristic three of LiMn2O4.Its theoretical capacity is about 278mAh/g, platform voltage reaches about 3.6V, discharge and recharge under 2.5-4.5V (vs.C) condition, has the discharge capacity of report to be stabilized at present and also reaches more than 180mAh/g into discharging under about 200mAh/g, 2.5-4.2V (vs.C).But its comparatively under high magnification (> 1C) specific discharge capacity still not high, add the existence still having Co, no matter be in fail safe, or at aspect of performance such as electric discharge limit, specific capacity etc., still having larger impact, is not still desirable anode material for lithium-ion batteries.
Existing have extensively research to adopt price is low, toxicity is little Ni, Mn, Co based material as lithium ion battery active material, particularly function admirable all there is layer structure Li 2mnO 3with LiMO 2the composite solid solution material xLi of (M=Ni, Mn, Co etc. one or more) 2mnO 3yLiMO 2, due to Li 2mnO 3with LiMO 2be easy to the solid-solution material that formation structure is dissolved each other, Li 2mnO 3in Li, Mn mixing layer be just evenly distributed in LiMO 2in the middle of, in theory, the Mn in mixing layer is+4 valencys, keeps valence state constant in charge and discharge process, plays support structure effect, makes LiMnO 2capacity closer to theoretical capacity, the battery of high power capacity can be prepared.This type of material of existing preparation generally adopts coprecipitation, solid phase method, sol-gal process etc., but these methods, or be that preparation condition is very harsh (as inert atmosphere, high temperature, high pressure, high-speed impact friction etc.), otherwise just easy reactant contact is incomplete; Be exactly that each component of presoma is uneven, can not ensure finally to generate the structure that product is design molecule, certainly also have other various shortcomings being unfavorable for producing in enormous quantities.Such as, disclose one in patent CN104362329 and prepare lithium-rich manganese-based Layered Lithium cell positive material based on efficient Solid complexing chemical reaction, comprise the following steps: first prepare to be used as the lithium source of raw material, nickel source, cobalt source and manganese source, prepare solid complex complexing agent; According to the metering ratio of each metallic element in the molecular formula of target product to be prepared lithium-rich manganese-based Layered Lithium cell positive material, the raw material of preparation and solid complex complexing agent are dry mixed evenly according to certain mol ratio, fully grind; The mixed material obtained is carried out drying at a lower temperature, obtains Solid complexing thing precursor; Solid complexing thing precursor is placed in air or oxygen-enriched atmosphere, sinters, obtain lithium-rich manganese-based Layered Lithium cell positive material.Method of the present invention is simple and easy to control, production cost is low, environmental protection, production efficiency is high, properties of product are excellent.But what it was prepared is only lithium-rich manganese-based Layered Lithium cell positive material, and its product prepared not is compound solid solution body structure, therefore, not there is the excellent properties of above-mentioned lithium-rich manganese-based layed solid-solution material.And admittedly the mixing dispersion in said method precursor power process is only consolidate-be dry mixed, and not only mixes heterogeneity, is unfavorable for the carrying out reacted; And, Gu admittedly-to be dry mixed, dry grinding often produces a large amount of and heat of instability, easily brings the material on container and ball milling pearl into, for the lot stability becoming to produce in enormous quantities has buried unstable hidden danger.
Summary of the invention
The present invention can not the technical problem of the lithium-rich manganese-based layed solid-solution of processability excellence preferably in order to overcome existing preparation method, provide a kind of can better the preparation method of lithium-rich manganese-based layed solid-solution of processability excellence and the lithium-rich manganese-based layed solid-solution of preparation thereof.
First object of the present invention is the preparation method in order to provide a kind of lithium-rich manganese-based layed solid-solution, and its step comprises: A, mixed in a solvent and disperse to obtain uniform mixed liquor in lithium source, manganese source, nickel source; B, by mixed liquor atomization drying, obtain presoma; C, by presoma under air atmosphere at 100 ~ 550 DEG C pre-burning 2 ~ 15h obtain pre-burning product; D, by step C gained pre-burning product under air atmosphere at 500 ~ 1100 DEG C calcine 5 ~ 20h obtain lithium-rich manganese-based layed solid-solution; Described lithium-rich manganese-based layed solid-solution is (1-2y) [xLi 2mnO 3(1 – x) LiNi 0.5mn 0.5o 2] yLiNi 1-xmn 1+xo 4, wherein, 0 < x < 1,0≤y < 1; Described lithium source, manganese source, nickel source are respectively the Li that can be dissolved in described solvent +, Mn 2+, Ni 2+metal organic/inorganic hydrochlorate, and the material that anionicsite in metal organic/inorganic hydrochlorate generates oxide when calcining under air atmosphere, can be sloughed; The actual use amount in described lithium source is 50% ~ 200% of theoretical amount.
Second object of the present invention is that this lithium-rich manganese-based layed solid-solution is obtained by the preparation method of above-mentioned lithium-rich manganese-based layed solid-solution in order to provide a kind of lithium-rich manganese-based layed solid-solution.
The present inventor finds to prepare lithium-rich manganese-based layed solid-solution by common methods such as existing coprecipitation, solid phase methods by long-term research, the lithium-rich manganese-based layed solid-solution performance of preparation is not good, the lithium-rich manganese-based layed solid-solution of desired result can not be obtained, and the present inventor seeks another kind of approach, adopt and prepare this material under liquid-phase condition, by method of the present invention, can by mixing very homogeneous for raw material, the reaction between raw material is more complete, homogeneous.The Li of the special ratios of obtained design that can be controlled 2mnO 3, LiNi 0.5mn 0.5o 2lamellar composite solid solution, even can also obtain stratiform Li 2mnO 3, LiNi 0.5mn 0.5o 2with a small amount of spinelle LiNi 1-xmn 1+xo 4the lamellar composite solid solution of compound, and the crystal formation of material is good, pattern is excellent, electrochemical performance, can significantly improve the performance of battery, and the raw material environmental protection used, cheap and easy to get, and preparation technology more for convenience, is applicable to producing in enormous quantities.
Accompanying drawing explanation
Fig. 1 is the process chart of the preferred embodiment of lithium-rich manganese-based layed solid-solution preparation method of the present invention.
The X ray diffracting spectrum of the lithium-rich manganese-based layed solid-solution sample of Fig. 2 prepared by embodiment 1.
The scanning electron microscope (SEM) photograph of the lithium-rich manganese-based layed solid-solution sample of Fig. 3 prepared by embodiment 1.
The constant current charge-discharge first circle circulation U-C that Fig. 4 a, Fig. 4 b are respectively 0.1C, 1C of the battery prepared by embodiment 1 schemes.
Fig. 5 a, Fig. 5 b are respectively the constant current charge and discharge cycle performance figure of 0.1C, 1C of the battery prepared by embodiment 1.
The X ray diffracting spectrum of the lithium-rich manganese-based layed solid-solution sample of Fig. 6 prepared by embodiment 2.
The scanning electron microscope (SEM) photograph of the lithium-rich manganese-based layed solid-solution sample of Fig. 7 prepared by embodiment 2.
The constant current charge-discharge first circle circulation U-C that Fig. 8 a, Fig. 8 b are respectively 0.1C, 1C of the battery prepared by embodiment 2 schemes.
Fig. 9 a, Fig. 9 b are respectively the constant current charge and discharge cycle performance figure of 0.1C, 1C of the battery prepared by embodiment 2.
The X ray diffracting spectrum of the lithium-rich manganese-based layed solid-solution sample of Figure 10 prepared by embodiment 3.
The scanning electron microscope (SEM) photograph of the lithium-rich manganese-based layed solid-solution sample of Figure 11 prepared by embodiment 3.
The constant current charge-discharge first circle circulation U-C that Figure 12 a, Figure 12 b are respectively 0.1C, 1C of the battery prepared by embodiment 3 schemes.
Figure 13 a, Figure 13 b are respectively the constant current charge and discharge cycle performance figure of 0.1C, 1C of the battery prepared by embodiment 3.
The X ray diffracting spectrum of the lithium-rich manganese-based layed solid-solution sample of Figure 14 prepared by embodiment 4.
The scanning electron microscope (SEM) photograph of the lithium-rich manganese-based layed solid-solution sample of Figure 15 prepared by embodiment 4.
The constant current charge-discharge first circle circulation U-C that Figure 16 a, Figure 16 b are respectively 0.1C, 1C of the battery prepared by embodiment 4 schemes.
Figure 17 a, Figure 17 b are respectively the constant current charge and discharge cycle performance figure of 0.1C, 1C of the battery prepared by embodiment 4.
The X ray diffracting spectrum of the lithium-rich manganese-based layed solid-solution sample of Figure 18 prepared by embodiment 5.
The scanning electron microscope (SEM) photograph of the lithium-rich manganese-based layed solid-solution sample of Figure 19 prepared by embodiment 5.
The constant current charge-discharge first circle circulation U-C that Figure 20 a, Figure 20 b are respectively 0.1C, 1C of the battery prepared by embodiment 5 schemes.
Figure 21 a, Figure 21 b are respectively the constant current charge and discharge cycle performance figure of 0.1C, 1C of the battery prepared by embodiment 5.
The X ray diffracting spectrum of the lithium-rich manganese-based layed solid-solution sample of Figure 22 prepared by embodiment 6.
The scanning electron microscope (SEM) photograph of the lithium-rich manganese-based layed solid-solution sample of Figure 23 prepared by embodiment 6.
The constant current charge-discharge first circle circulation U-C that Figure 24 a, Figure 24 b are respectively 0.1C, 1C of the battery prepared by embodiment 6 schemes.
Figure 25 a, Figure 25 b are respectively the constant current charge and discharge cycle performance figure of 0.1C, 1C of the battery prepared by embodiment 6.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of preparation method of lithium-rich manganese-based layed solid-solution, its step comprises: lithium source, manganese source, nickel source mix and disperse to obtain uniform mixed liquor by A in a solvent; B, by mixed liquor spraying dry, obtain presoma; C, by presoma under air atmosphere at 100 ~ 550 DEG C pre-burning 2 ~ 15h obtain pre-burning product; D, by step C gained pre-burning product under air atmosphere at 500 ~ 1100 DEG C calcine 5 ~ 20h obtain lithium-rich manganese-based layed solid-solution; Wherein, lithium-rich manganese-based layed solid-solution is (1-2y) [xLi 2mnO 3(1 – x) LiNi 0.5mn 0.5o 2] yLiNi 1-xmn 1+xo 4, wherein, 0 < x < 1,0≤y < 1.
Generally, in the lithium source of mixing, manganese source, nickel source for in the molecular formula of material that need prepare
The actual use amount in lithium source is 50% ~ 200% of theoretical amount, and namely the actual throwing lithium amount in lithium source is containing lithium amount in the molecular formula of the material that need prepare 50% ~ 200% in the preparation.
Preferably, the actual use amount in lithium source is 95% ~ 100% of theoretical amount, can improve the high rate performance of the material of preparation further.
Or preferably, the actual use amount in lithium source is 100% ~ 110% of theoretical amount, improve specific discharge capacity and the cyclical stability of the material of preparation further.
In steps A by lithium source, manganese source, nickel source mixes in a solvent can be added in same solvent in lithium source, manganese source, nickel source etc. to dissolve; Also can be by lithium source solution, manganese source solution, the mixing of nickel source solution.Disperse to obtain homogeneous mixed liquor, homogeneous mixed liquor can be homogeneous clear transparent solutions, also can be the suspension-turbid liquid, emulsion, colloid etc. of homogeneous dispersion; Mode the present invention of dispersion does not limit, can be the well-known various process for dispersing of art technology, such as, can be mechanical agitation (comprising the paddle etc. of stirrer, paddle, band jet effect), the dispersion of ultrasonic disperse, ball milling, nano-level grinder dispersion etc.Solvent can be water.Concrete steps A can for get corresponding lithium source, manganese source, nickel source according to metering score another name, uses water as lithium source that dissolution with solvents takes, manganese source, nickel source successively, and be made into mixing clear aqueous solution in same container, and maintain and be stirred to homogeneous solution;
The homogeneous mixed liquor of above-mentioned specific components is by atomization drying of the present invention, and solvent is by rapid evaporate to dryness, and obtained powder not easily absorbs water, and performance is better, and wherein, atomization drying the present invention do not limit, and is preferably spraying dry.
Wherein, lithium-rich manganese-based layed solid-solution of the present invention is (1-2y) [xLi 2mnO 3(1 – x) LiNi 0.5mn 0.5o 2] yLiNi 1-xmn 1+xo 4, wherein, 0 < x < 1,0≤y < 1, it is Li 2mnO 3, LiNi 0.5mn 0.5o 2, LiNi 1-xmn 1+xo 4lamellar composite solid solution.There is special structure, and find Li through large quantity research 2mnO 3the cyclical stability of material can be improved, LiNi 0.5mn 0.5o 2the high rate performance of material can be improved, LiNi 1-xmn 1+xo 4the charging/discharging voltage of material can be improved thus promote reversible capacity further, the composite solid solution of this two or three material can not only play separately the performance of each material, and the interaction between the structure of matter, the performance of material can be improved further, by the composite solid solution of this structure of preparation that method of the present invention can be controlled, and the material crystal formation of preparation is excellent, excellent performance.
Preferably, obtained lithium-rich manganese-based layed solid-solution is 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2, method of the present invention preparation preferably this kind of material, and 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2under the multiplying power of below 1C, specific discharge capacity and cyclical stability are all better.
Lithium source, manganese source, nickel source are respectively the Li that can be dissolved in selected solvent +, Mn 2+, Ni 2+metal organic/inorganic hydrochlorate, and the anionicsite can sloughed when calcining under air atmosphere in metal organic/inorganic hydrochlorate generates the material of oxide, concrete lithium source, manganese source, the present invention of nickel source do not limit, the various lithium sources that can be known to the skilled person, manganese source, nickel source, the present invention is preferred, and lithium source is citric acid-lithium hydroxide; Manganese source is manganese acetate; Nickel source is nickel acetate.Citric acid can not only complexation of metal ions, and neutralization alkalescence is played a part to whole solution system, because of lithium hydroxide easily and metal ion formed and precipitate, the present invention preferably uses the organic acid ion such as citric acid, acetate anion effectively can stop the generation of precipitation, the uniform solution system of the whole reaction of further guarantee, and citric acid-lithium hydroxide, manganese acetate, nickel acetate are all soluble in water, wide material sources, stay in grade, with low cost.
Preferably, in citric acid-lithium hydroxide, the mol ratio of citric acid and lithium hydroxide is 1/3 ~ 1; Further preferably, in citric acid-lithium hydroxide, the mol ratio of citric acid and lithium hydroxide is 2/3 ~ 1, and the material comprehensive electrochemical of preparation is better.
Temperature selected by spraying dry is then on the boiling point of selected solvent, and will ensure that solute side reaction does not occur and do not decompose.Preferably, because volatile solvent that the present invention is used is nontoxic water with low cost, and containing reacted acylate in water, preferably, spray-dired temperature is 100 DEG C ~ 200 DEG C, obtains shallow green powder.
Pre-burning, generally in Muffle furnace, generally needs to ensure sample abundant and air haptoreaction under assigned temperature.Preferably, the temperature of pre-burning is 200 DEG C ~ 550 DEG C, and the time is 2 ~ 5h, improves the performance of material further.
Calcine also general in Muffle furnace, the temperature of preferably calcining is 650 ~ 1050 DEG C, and more preferably 650 ~ 950 DEG C, the time is 8 ~ 15h.
For improving the performance of material further, preferably in material surface carbon coated, preparation method of the present invention is preferred, also comprise between step C and step D and carbon source and pre-burning product are mixed into homogeneous mixed liquor in a solvent, the pre-burning product that dry carbon source is coated under homodisperse state, then by pre-burning product coated for carbon source calcining through step D the coated lithium-rich manganese-based layed solid-solution of carbon.
Concrete can be pulverize pre-burning product, makes the particle diameter of particle be less than 74um the best.Then carbon source and pre-burning product are joined in solvent, be configured to suspension-turbid liquid, and to be mixed to solid-liquid two-phase be homogeneous color, obtain the pre-burning product that carbon source is coated.By above-mentioned suspension-turbid liquid under the state stirred, pulverize and can carry out follow-up calcining step after heating evaporate to dryness.Wherein, pulverizing can adopt the breaking methods such as grinding, ball milling, high-energy ball milling, pulverizer, airflow milling, and preferably, low dose can consider mortar and pulverizer, and heavy dose then can consider pulverizer and airflow milling.
Wherein, carbon source is carbonaceous organic material, such as, can be carbohydrate, organic acid, organic high molecular polymer etc.Carbohydrate can be selected from one or more in monose, disaccharides or polysaccharide.Monose can be one or more in galactolipin, glucose or fructose; Disaccharides can be sucrose, lactose, maltose etc.; Polysaccharide can be starch, cellulose, glycogen, glycoprotein, Arabic gum, deoxyribose etc.Preferably, carbon source is one or more in glucose, maltose, sucrose or starch, wide material sources, cheap, stay in grade.
Preferably, the amount of coated carbon source is 0 ~ 40wt% of pre-burning product; Further preferably, the amount of described coated carbon source is the 2wt% ~ 20wt% of pre-burning product.
Wherein, solvent the present invention do not limit, the various solvents that can be known to the skilled person, such as water, ethanol, methyl alcohol, acetone etc.Preferably, water and ethanol, improve the fail safe of production and reduce costs.
Wherein, homogeneous mixed liquor can be suspension-turbid liquid, also can be consoluet solution, also can be low viscous colloid etc.
The mode of dispersion comprises: mechanical agitation (comprising the paddle etc. of stirrer, paddle, band jet effect), the dispersion of ultrasonic disperse, ball milling, nano-level grinder etc.
Wherein, step D has calcined rear generally need and has cooled, and can be placed in furnace chamber naturally to cool; Also can be take out at once after burning down, then cool (quenching) under room temperature environment; Can also be cooled gradually according to certain cooldown rate by the programmed cooling function setting of stove; Even can also be cooled rapidly by it by supercool media such as liquid nitrogen.Take out at once after the present invention has preferably calcined, adopt the mode of quenching to cool, optimize the performance of material further.
A kind of embodiment that method of the present invention is concrete can consult Fig. 1, is the process chart of the preferred embodiment of lithium-rich manganese-based layed solid-solution preparation method of the present invention, as shown in Figure 1.
Invention also provides a kind of lithium-rich manganese-based layed solid-solution, this lithium-rich manganese-based layed solid-solution is obtained by the preparation method of above-mentioned lithium-rich manganese-based layed solid-solution.It can as the positive electrode active materials of lithium ion battery, as present emerging positive electrode, and electrochemical performance.
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
According to 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2metering score another name get 1.176molLiOH (actual throw lithium amount be 100% of theory lithium amount), 0.392mol citric acid, 0.6molMnAc 24H 2o, 0.2molNiAc 24H 2o, dissolves the LiOH, citric acid, the MnAc that take successively in same container 24H 2o, NiAc 24H 2o, and (it is the material 0.5Li that need prepare to be made into 1.0mol/L 2mnO 30.5LiNi 0.5mn 0.5o 2molar concentration) mix green clear aqueous solution, wherein green settled solution peristaltic pump is sucked spray dryer, after spraying dry, obtains presoma.Take 2g presoma and put into box Muffle furnace, in air atmosphere with pre-burning 2h at 400 DEG C, burn down and naturally cool to room temperature.The sample of above pre-burning to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Again put into Muffle furnace at 850 DEG C of calcining 12h, take out quenching to room temperature, obtained lithium-rich manganese-based layed solid-solution sample S1.
Carry out X-ray powder diffraction test by the X-ray diffractometer of German BRUKER company D8ADVANCE model to sample S1, be illustrated in figure 2 the X-ray diffractogram of sample S1, can analyze sample S1 from figure is Li 2mnO 3and Li 1.15(Mn xni 1-x) 0.85o 2composite solid solution.
By the ESEM of HIT S-3400N model, scanning electron microscope observation is carried out to sample S1, be illustrated in figure 3 the scanning electron microscope (SEM) photograph of sample S1, can analyze from figure that sample S1 pattern is good, crystal formation is excellent.
According to sample S1: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, with the Xin Zhou nation LBC-315 electrolyte of 1mol/L, assembling button cell.
Battery is carried out electrochemical property test on Land BS9300 (Wuhan gold promise electronics) program control automatic electrochemical test, constant current charge-discharge is carried out respectively with 0.1C, 1C electric current, the constant current charge-discharge first circle circulation U-C of the battery of test schemes respectively as Fig. 4 a, Fig. 4 b, and the constant current charge and discharge cycle performance figure of battery is as Fig. 5 a, Fig. 5 b.
Embodiment 2
According to 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2take corresponding 1.2molLiOH (actual throwing lithium amount is 102% of theory lithium amount) respectively, 0.4mol citric acid, 0.6molMnAc 24H 2o, 0.2molNiAc 24H 2o, dissolves the lithium source taken, manganese source, nickel source successively in same container, and the green clear aqueous solution of the mixing being made into 1.0mol/L, wherein green settled solution peristaltic pump is sucked spray dryer, after spraying dry, obtains forerunner's product.Take 2g presoma and put into box Muffle furnace, in air atmosphere with pre-burning 2h at 400 DEG C, burn down and naturally cool to room temperature.The sample of above pre-burning to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Again put into Muffle furnace at 850 DEG C of calcining 12h, take out quenching to room temperature, obtained lithium-rich manganese-based layed solid-solution sample S2.
Adopt the method identical with embodiment 1 to record the X-ray diffractogram of sample S2 as Fig. 6, sample S2 can be analyzed contain Li from figure 2mnO 3and Li 1.15(Mn xni 1-x) 0.85o 2composite solid solution.Scanning electron microscope (SEM) photograph is as Fig. 7.
According to sample S2: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, with the Xin Zhou nation LBC-315 electrolyte of 1mol/L, assembling button cell.
The constant current charge-discharge first circle circulation U-C adopting the method identical with embodiment 1 to record above-mentioned obtained battery schemes respectively as Fig. 8 a, Fig. 8 b, and the constant current charge and discharge cycle performance figure of battery is as Fig. 9 a, Fig. 9 b.
Embodiment 3
According to 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2take corresponding 1.224molLiOH (actual throwing lithium amount is 102% of theory lithium amount) respectively, 0.408mol citric acid, 0.6molMnAc 24H 2o, 0.2molNiAc 24H 2o, dissolves the lithium source taken, manganese source, nickel source successively in same container, and the green clear aqueous solution of the mixing being made into 1.0mol/L, wherein green settled solution peristaltic pump is sucked spray dryer, after spraying dry, obtains forerunner's product.Take 2g presoma and put into box Muffle furnace, in air atmosphere with pre-burning 2h at 400 DEG C, burn down and naturally cool to room temperature.The sample of above pre-burning to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Again put into Muffle furnace at 850 DEG C of calcining 12h, take out quenching to room temperature, obtained lithium-rich manganese-based layed solid-solution sample S3.
Adopt the method identical with embodiment 1 to record the X-ray diffractogram of sample S3 as Figure 10, sample S3 can be analyzed contain Li from figure 2mnO 3and Li 1.15(Mn xni 1-x) 0.85o 2composite solid solution.Scanning electron microscope (SEM) photograph is as Figure 11.
According to sample S3: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, with the Xin Zhou nation LBC-315 electrolyte of 1mol/L, assembling button cell.
The constant current charge-discharge first circle circulation U-C adopting the method identical with embodiment 1 to record above-mentioned obtained battery schemes respectively as Figure 12 a, Figure 12 b, and the constant current charge and discharge cycle performance figure of battery is as Figure 13 a, Figure 13 b.
Embodiment 4
According to 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2take corresponding 1.224molLiOH (actual throwing lithium amount is 102% of theory lithium amount) respectively, 0.816mol citric acid, 0.6molMnAc 24H 2o, 0.2molNiAc 24H 2o, dissolves the lithium source taken, manganese source, nickel source successively in same container, and the green clear aqueous solution of the mixing being made into 1.0mol/L, wherein green settled solution peristaltic pump is sucked spray dryer, after spraying dry, obtains forerunner's product.Take 2g presoma and put into box Muffle furnace, in air atmosphere with pre-burning 3h at 350 DEG C, burn down and naturally cool to room temperature.The sample of above pre-burning to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Again put into Muffle furnace at 950 DEG C of calcining 12h, take out quenching to room temperature, obtained lithium-rich manganese-based layed solid-solution sample S4.
Adopt the method identical with embodiment 1 to record the X-ray diffractogram of sample S4 as Figure 14, sample S4 can be analyzed contain Li from figure 2mnO 3and Li 1.15(Mn xni 1-x) 0.85o 2composite solid solution.Scanning electron microscope (SEM) photograph is as Figure 15.
According to sample S4: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, with the Xin Zhou nation LBC-315 electrolyte of 1mol/L, assembling button cell.
The constant current charge-discharge first circle circulation U-C adopting the method identical with embodiment 1 to record above-mentioned obtained battery schemes respectively as Figure 16 a, Figure 16 b, and the constant current charge and discharge cycle performance figure of battery is as Figure 17 a, Figure 17 b.
Embodiment 5
According to 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2take corresponding 1.224molLiOH (actual throwing lithium amount is 102% of theory lithium amount) respectively, 1.224mol citric acid, 0.6molMnAc 24H 2o, 0.2molNiAc 24H 2o, dissolves the lithium source taken, manganese source, nickel source successively in same container, and the green clear aqueous solution of the mixing being made into 1.0mol/L, wherein green settled solution peristaltic pump is sucked spray dryer, after spraying dry, obtains forerunner's product.Take 2g presoma and put into box Muffle furnace, in air atmosphere with pre-burning 3h at 350 DEG C, burn down and naturally cool to room temperature.The sample of above pre-burning to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Again put into Muffle furnace at 950 DEG C of calcining 12h, take out quenching to room temperature, obtained lithium-rich manganese-based layed solid-solution sample S5.
Adopt the method identical with embodiment 1 to record the X-ray diffractogram of sample S5 as Figure 18, sample S5 can be analyzed contain Li from figure 2mnO 3and Li 1.15(Mn xni 1-x) 0.85o 2composite solid solution.Scanning electron microscope (SEM) photograph is as Figure 19.
According to sample S5: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, with the Xin Zhou nation LBC-315 electrolyte of 1mol/L, assembling button cell.
The constant current charge-discharge first circle circulation U-C adopting the method identical with embodiment 1 to record above-mentioned obtained battery schemes respectively as Figure 20 a, Figure 20 b, and the constant current charge and discharge cycle performance figure of battery is as Figure 21 a, Figure 21 b.
Embodiment 6
According to 0.5Li 2mnO 30.5LiNi 0.5mn 0.5o 2take corresponding 1.224molLiOH (actual throwing lithium amount is 102% of theory lithium amount) respectively, 1.224mol citric acid, 0.6molMnAc 24H 2o, 0.2molNiAc 24H 2o, dissolves the lithium source taken, manganese source, nickel source successively in same container, and the green clear aqueous solution of the mixing being made into 1.0mol/L.Green settled solution peristaltic pump is sucked spray dryer, after spraying dry, obtains presoma.Take 2g presoma and put into box Muffle furnace, in air atmosphere with pre-burning 3h at 300 DEG C, burn down and naturally cool to room temperature.The sample of above pre-burning to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Presoma is dried 8 ~ 72 hours at 80 DEG C as in baking oven, moisture unnecessary in removing presoma.Glucose and presoma are added to the water, are configured to suspension-turbid liquid, and to be mixed to solid-liquid two-phase be homogeneous color, obtain the coated presoma suspension-turbid liquid of material with carbon element; By suspension-turbid liquid under the state stirred, heating evaporate to dryness.Scrape the sample after evaporate to dryness and by the mixture of the coated presoma of material with carbon element after mixing at 200 ~ 250 DEG C of drying 2 ~ 4h, solvent evaporated completely and makes coated carbon-coating that reaction to a certain degree occur and obtain the mixture of the coated presoma of low-temperature carbonization material with carbon element.The mixture of coated for low-temperature carbonization material with carbon element presoma to be taken out and levigate mill is even, and guaranteed 200 order sample sifters.Again put into Muffle furnace at 950 DEG C of calcining 12h, take out quenching to room temperature, obtained lithium-rich manganese-based layed solid-solution sample S6.
Adopt the method identical with embodiment 1 to record the X-ray diffractogram of sample S6 as Figure 22, sample S6 can be analyzed contain Li from figure 2mnO 3and Li 1.15(Mn xni 1-x) 0.85o 2composite solid solution.Scanning electron microscope (SEM) photograph is as Figure 23.
According to sample S6: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, with the Xin Zhou nation LBC-315 electrolyte of 1mol/L, assembling button cell.
The constant current charge-discharge first circle circulation U-C adopting the method identical with embodiment 1 to record above-mentioned obtained battery schemes respectively as Figure 24 a, Figure 24 b, and the constant current charge and discharge cycle performance figure of battery is as Figure 25 a, Figure 25 b.
Comparative example 1
The method step in the embodiment 2 of patent CN104362329 is adopted to prepare positive electrode active materials sample DS2, the method identical with embodiment 5 is adopted to prepare battery, be sample DS2 unlike positive electrode active materials, and the multiplying power electric current of its battery charging and discharging test is 12.5mA/g, this is just equivalent to the charge-discharge magnification being less than 0.05C.The constant current charge-discharge first circle circulation U-C adopting the method identical with embodiment 5 to record above-mentioned obtained battery schemes (D Fig. 2) and can find out that the first circle specific discharge capacity of DS2 is about 232mAh/g, and the 0.1C multiplying power first circle specific discharge capacity of S5 is 242.2mAh/g, and the product S 6 of embodiment 6 gained of coated carbon of the present invention, it carries out the charge-discharge test of 0.1C according to same step, its first circle specific discharge capacity up to 270.1mAh/g, the theoretical capacity of closely 286mAh/g.
The crystal formation of material prepared by the present invention is good, pattern is excellent, electrochemical performance, can significantly improve the performance of battery, and the raw material environmental protection, cheap and easy to get used, preparation technology more for convenience, is applicable to producing in enormous quantities.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection range that all should belong to claims of the present invention.

Claims (10)

1. a preparation method for lithium-rich manganese-based layed solid-solution, is characterized in that, step comprises:
A, lithium source, manganese source, nickel source are mixed in a solvent and disperse to obtain uniform mixed liquor;
B, by mixed liquor atomization drying, obtain presoma;
C, by presoma under air atmosphere at 100 ~ 550 DEG C pre-burning 2 ~ 15h obtain pre-burning product;
D, by step C gained pre-burning product under air atmosphere at 500 ~ 1100 DEG C calcine 5 ~ 20h obtain lithium-rich manganese-based layed solid-solution;
Described lithium-rich manganese-based layed solid-solution is (1-2y) [xLi 2mnO 3(1 – x) LiNi 0.5mn 0.5o 2] yLiNi 1-xmn 1+xo 4, wherein, 0 < x < 1,0≤y < 1;
Described lithium source, manganese source, nickel source are respectively the Li that can be dissolved in described solvent +, Mn 2+, Ni 2+metal organic/inorganic hydrochlorate, and the material that anionicsite in metal organic/inorganic hydrochlorate generates oxide when calcining under air atmosphere, can be sloughed;
The actual use amount in described lithium source is 50% ~ 200% of theoretical amount.
2. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 1, it is characterized in that, the actual use amount in described lithium source is 95% ~ 100% of theoretical amount.
3. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 1, it is characterized in that, the actual use amount in described lithium source is 100% ~ 110% of theoretical amount.
4. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 1, it is characterized in that, described lithium source is citric acid-lithium hydroxide; Manganese source is manganese acetate; Nickel source is nickel acetate.
5. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 4, it is characterized in that, in described citric acid-lithium hydroxide, the mol ratio of citric acid and lithium hydroxide is 1/3 ~ 1.
6. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 5, it is characterized in that, in described citric acid-lithium hydroxide, the mol ratio of citric acid and lithium hydroxide is 2/3 ~ 1.
7. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 1, is characterized in that,
The mode of described dispersion is selected from one or more in mechanical agitation, ultrasonic disperse, ball milling dispersion or nano-level grinder dispersion;
Described atomization drying is spraying dry, and described spray-dired temperature is 70 DEG C ~ 200 DEG C;
The temperature of described pre-burning is 200 DEG C ~ 550 DEG C, and the time is 2 ~ 5h;
The temperature of described calcining is 650 ~ 1050 DEG C, and the time is 8 ~ 15h.
8. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 1, it is characterized in that, also comprise between described step C and step D and carbon source and pre-burning product are mixed into homogeneous mixed liquor in a solvent, the pre-burning product that dry carbon source is coated under homodisperse state, then by pre-burning product coated for carbon source calcining through step D the coated lithium-rich manganese-based layed solid-solution of carbon;
Described carbon source is carbonaceous organic material;
The amount of described coated carbon source is 0 ~ 40wt% of pre-burning product; Preferably, the amount of described coated carbon source is the 2wt% ~ 20wt% of pre-burning product.
9. the preparation method of lithium-rich manganese-based layed solid-solution according to claim 1, is characterized in that, take out at once after described step D has calcined, and adopts the mode of quenching to cool.
10. a lithium-rich manganese-based layed solid-solution, is characterized in that, described lithium-rich manganese-based layed solid-solution is obtained by the preparation method of the lithium-rich manganese-based layed solid-solution in claim 1-9 described in any one.
CN201510176568.3A 2015-04-15 2015-04-15 Preparation method for rich lithium manganese layered solid solution and rich lithium manganese layered solid solution prepared by adopting preparation method Pending CN104795546A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510176568.3A CN104795546A (en) 2015-04-15 2015-04-15 Preparation method for rich lithium manganese layered solid solution and rich lithium manganese layered solid solution prepared by adopting preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510176568.3A CN104795546A (en) 2015-04-15 2015-04-15 Preparation method for rich lithium manganese layered solid solution and rich lithium manganese layered solid solution prepared by adopting preparation method

Publications (1)

Publication Number Publication Date
CN104795546A true CN104795546A (en) 2015-07-22

Family

ID=53560203

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510176568.3A Pending CN104795546A (en) 2015-04-15 2015-04-15 Preparation method for rich lithium manganese layered solid solution and rich lithium manganese layered solid solution prepared by adopting preparation method

Country Status (1)

Country Link
CN (1) CN104795546A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108172823A (en) * 2018-01-26 2018-06-15 浙江吉利汽车研究院有限公司 Rich lithium manganese material, anode material for lithium-ion batteries, based lithium-ion battery positive plate, lithium ion battery and preparation method thereof
CN114497528A (en) * 2021-12-29 2022-05-13 无锡晶石新型能源股份有限公司 Method for preparing lithium-rich manganese-based solid solution by spray drying and oxygen-rich sintering

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡伟等: ""0.5Li2MnO3•0.5LiMn0.5Ni0.5O2的合成及电化学性能"", 《世界有色金属》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108172823A (en) * 2018-01-26 2018-06-15 浙江吉利汽车研究院有限公司 Rich lithium manganese material, anode material for lithium-ion batteries, based lithium-ion battery positive plate, lithium ion battery and preparation method thereof
CN108172823B (en) * 2018-01-26 2021-05-25 浙江吉利汽车研究院有限公司 Lithium-manganese-rich material, lithium ion battery positive electrode plate, lithium ion battery and preparation method thereof
CN114497528A (en) * 2021-12-29 2022-05-13 无锡晶石新型能源股份有限公司 Method for preparing lithium-rich manganese-based solid solution by spray drying and oxygen-rich sintering

Similar Documents

Publication Publication Date Title
CN103119761B (en) Active material for lithium secondary battery, electrode of lithium secondary cell and lithium secondary battery
Tang et al. Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2
CN101409342B (en) Method for preparing composite anode material
CN102738458B (en) Surface modification method of lithium-rich cathode material
CN101908624B (en) Positive pole material of secondary lithium battery and preparation method thereof
CN102437323A (en) Anode material of lithium ion battery and preparation method thereof
CN104051724A (en) Carbon-coated nickel-cobalt lithium manganate positive electrode material and preparation method thereof
CN1838453A (en) Lithium-nickel-cobalt-manganese-oxygen material for lithium ion battery positive electrode and preparation method thereof
CN102569773B (en) Anode material for lithium-ion secondary battery and preparation method thereof
CN109873140B (en) Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material
CN101699639A (en) Method for preparing carbon-coated nano-grade lithium iron phosphate composite anode material
CN103887483A (en) Doped and modified ternary positive electrode material and preparation method thereof
CN105609758A (en) Preparation method of rubdium- and cesium-doped lithium-rich ternary cathode material for lithium-ion battery
CN107785551A (en) The lithium-rich oxide material and preparation method of a kind of phase structure ratio gradient
CN106910887A (en) A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode
CN102263238A (en) Lithium nickel cobalt manganese oxide and preparation method thereof
CN106025208A (en) Preparation method for carbon-coated ternary positive electrode material
CN102931394B (en) Lithium nickel manganese oxide material and preparation method thereof, lithium ion battery containing this material
CN102531071A (en) Method for preparing lithium ion battery anode material LiNi0.5Mn1.5O4
CN108091854A (en) A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof
CN104979549A (en) 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
CN102664255B (en) Lithium nickel manganese oxide material and preparation method thereof, lithium ion battery containing this material
CN104022282A (en) High temperature solid state preparation method of lithium ion battery cathode material lithium metasilicate
CN106207158A (en) The preparation method of rich lithium manganate cathode material for lithium
CN103367733A (en) Lithium ion battery cathode material and preparation method thereof and lithium ion battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150722