CN105702951A - Multiple-linkage modified lithium-rich manganese-based material and modification method thereof - Google Patents
Multiple-linkage modified lithium-rich manganese-based material and modification method thereof Download PDFInfo
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- CN105702951A CN105702951A CN201610235018.9A CN201610235018A CN105702951A CN 105702951 A CN105702951 A CN 105702951A CN 201610235018 A CN201610235018 A CN 201610235018A CN 105702951 A CN105702951 A CN 105702951A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a modification method of a multiple-linkage modified lithium-rich manganese-based material. The modification method is characterized by comprising the steps as follows: a surface coating material of the lithium-rich manganese-based material forms a coating layer; the material contains transition metal elements; the targets that partial lithium ions in the lithium-rich manganese-based material are deintercalated in advance, enter the coating layer and react with the material in the coating layer to generate a lithium-containing compound are achieved through a thermal treatment technology; meanwhile, partial transition metal elements in the coating layer enter the lithium-rich manganese-based material to form bulk phase doping; and finally the bulk phase-doped/surface-coated/pre-deintercalated 'multiple-linkage' modified material is obtained. The lithium-rich manganese-based material provided by the invention has good rate capability and good cycle performance; the preparation technology is simple; the cost is low; and the application prospect is wide.
Description
Technical field
The present invention relates to lithium ion battery material technical field, be specifically related to the modified lithium-rich anode material of a kind of multiple linkage and method of modifying thereof。
Background technology
Since the industrial revolution, human material's civilization obtains tremendous development, and the demand of the energy is grown with each passing day。Based on the environmental cost (greenhouse effect, PM2.5 etc.) that finiteness and the use thereof of fossil fuel resource bring, people are forced to find other clean reproducible energies, for instance hydroelectric generation, solar electrical energy generation and wind-power electricity generation etc.。But above-mentioned clean reproducible energy by extraneous factor affect relatively big (such as, solar electrical energy generation was affected greatly by season, the meteorological condition such as round the clock and rain or shine), can not the generating of continuous and stable, be provided out electric power while steady and continuous can be realized as being used in combination with energy storage device (energy storage and peak regulation etc.)。Additionally, at the use end (3C Product and electric automobile etc.) of the energy, it is necessary to energy accumulating device with the use of。And lithium ion battery obtains concern and the research of global range as a kind of important energy storage device。Lithium ion battery relatively other traditional chemical power supplys (such as lead-acid battery, Ni-MH battery etc.) have energy density height, power density is big, have extended cycle life and the distinguishing feature such as environmental friendliness, thus becoming environment-friendly type secondary cell most with prospects。
The capacity of commercial negative material is at 300～400mAhg at present-1Left and right, at the substitution material capacity of conceptual phase especially up to 1000～2000mAhg-1Left and right。And commercialization positive electrode actual discharge specific capacity is all at 200mAhg-1Hereinafter, the positive electrode therefore finding a kind of more high power capacity is extremely urgent。1999, Johnson etc. used the method for weak-acid leaching to make part Li2O is from Li2MnO3Deviate from mutually, obtain with Li first2MnO3Carry out the LiMnO of rock-steady structure2(Li2-xMnO3-x/2, wherein 0 < x < 2)。Lithium-rich manganese base material xLi2MnO3·(1-x)LiMO2(M=Mn, Co, Ni, Al, etc.) capacity is up to 250～300mAhg-1, far above the capacity of existing commercial batteries positive electrode, the manganese element in lithium-rich manganese base material accounts for relatively larger simultaneously, reduce further material cost, thus becoming the study hotspot of high-capacity lithium-ion positive electrode。But the problems such as lithium-rich manganese base material has, and electronics/lithium ion transport ability, cycle performance be poor, voltage attenuation and manganese dissolving, coulombic efficiency is very low especially first, hinders the business application of lithium-rich anode material。Therefore, lithium-rich manganese base material is modified research to be extremely necessary。
The modified of lithium-rich manganese base material are adopted single bulk phase-doped, Surface coating or structural design that it is modified by current Chinese scholars more。Only the seminar of only a few can adopt two kinds of methods that lithium-rich manganese base material is modified simultaneously。So make the modified of lithium-rich manganese base material is limited to very much, even appear in and the otherwise performance of lithium-rich manganese base material when improving lithium-rich manganese base material aspect performance, can be damaged。
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming prior art to exist, a kind of method that can simultaneously from many aspects lithium-rich manganese base material be modified and corresponding material are provided, modified lithium-rich manganese base material is made to have both good high rate performance and good cycle performance, electrolyte resistance burn into coulombic efficiency first high, lithium-rich manganese base material that modified technique is simple, cost is low, application prospect is wide simultaneously a kind of multiple linkage is modified and method of modifying thereof。
For solving above-mentioned technical problem, the present invention by the following technical solutions:
The method of modifying of the lithium-rich manganese base material that a kind of multiple linkage is modified, it is characterized in that, including: the Surface coating material in lithium-rich manganese base material forms clad, containing transition metal in described material, realize part lithium ion in lithium-rich manganese base material by Technology for Heating Processing to deviate to enter clad in advance, react generation lithium-containing compound with the material in clad, being formed bulk phase-doped in section transitions metallic element entrance lithium-rich manganese base material in clad, " multiple-linkage " that finally give bulk phase-doped/Surface coating/pre-de-lithium is material modified simultaneously。
Preferably, the molecular formula of described lithium-rich manganese base material is Li1+x[NiaCobMn(1-a-b)]1-xO2, in formula, 0.1 < x < 1,0≤a < 1,0≤b < 1,0 < a+b < 1。
It is highly preferred that described lithium-rich manganese base material is hollow-core construction。
Preferably, it is solvent evaporated method, hydro-thermal method, magnetron sputtering method, vapour deposition process, coprecipitation, sol-gal process, spray drying method or spray pyrolysis that the described Surface coating material in lithium-rich manganese base material forms the method for clad。
More preferably, described solvent evaporated method includes: the preparation solution containing transition metal, lithium-rich manganese base material is distributed in the solution that above-mentioned configuration is good, control appropriate solids content, under agitation, maintenance system temperature, at 40-100 DEG C, forms clad by solvent evaporation at lithium-rich manganese base material Surface coating material。
It is furthermore preferred that described solids content controls at 2-80%。
Preferably, the described material in clad is more than one in the salt of transition metal, oxide, hydroxide and amorphous amorphous substance。
Preferably, containing more than one transition metals in the described material in clad。
Preferably, the described material in clad and lithium-rich manganese base material mass ratio between 3: 1 to 1: 100。
Preferably, described Technology for Heating Processing is multistage temperature control calcining。
Preferably, described Technology for Heating Processing includes first calcining 2～65 hours at 200 DEG C～700 DEG C, then calcines 1～80 hour at 300 DEG C～1000 DEG C。
Present invention also offers the lithium-rich manganese base material that the prepared multiple linkage of the method for modifying of the modified lithium-rich manganese base material of above-mentioned multiple linkage is modified。
Compared with prior art, it is an advantage of the current invention that: by lithium-rich anode material coated with uniform layer of substance, after suitable Technology for Heating Processing, part lithium ion in lithium-rich manganese base material can be realized deviate to enter clad in advance, react generation lithium-containing compound with the material in clad, clad is formed bulk phase-doped in part transition metal entrance matrix material simultaneously, finally give the de-lithium of bulk phase-doped/Surface coating/in advance " multiple-linkage " material modified, thus improving the cycle performance of lithium-rich anode material, high rate performance, electrolyte resistance corrosive power, coulombic efficiency etc. first。Comprehensive, the chemical property of this positive electrode obtains and is greatly promoted, and compensate for conventional rich lithium material method of modifying and can not take into account many-sided simultaneously modified deficiency, may advantageously facilitate the commercialization of lithium ion battery high power capacity positive electrode。Lithium-rich manganese base material of the present invention has both good high rate performance and good cycle performance simultaneously, and its preparation technology is simple, cost is low, application prospect is wide
Accompanying drawing explanation
Fig. 1 is the SEM figure of lithium-rich anode material after the multiple linkage before modified that the embodiment of the present invention 1 prepares。A () is the microscopic appearance figure of lithium-rich manganese base material before modified, (b) is the microscopic appearance figure of the modified lithium-rich manganese base material of multiple linkage, and (c) is the EDS elementary analysis figure in region, multiple linkage modified lithium-rich manganese base material surface；
Fig. 2 is the XRD figure of lithium-rich anode material after the multiple linkage before modified that the embodiment of the present invention 1 prepares。A the diffracting spectrum between () 10-80 °, (b) is the diffracting spectrum between 20-30 °；
Fig. 3 is the charge-discharge property comparison diagram of lithium-rich anode material after the multiple linkage before modified that the embodiment of the present invention 1 prepares。
Fig. 4 be the modified lithium-rich anode material for preparing of the embodiment of the present invention 1 with pure phase lithium-rich anode material at 250mAg-1The cycle performance comparison diagram of current charge-discharge electricity。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further。Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention。In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally。
Heretofore described " multiple-linkage " refers to bulk phase-doped, Surface coating and pre-de-three kinds of modification mode of lithium realize simultaneously。
In the present invention, all percent concentrations if no special instructions, are weight percent concentration。
Embodiment 1
The method of modifying of the lithium-rich manganese base material that a kind of multiple linkage is modified, concretely comprises the following steps:
(1) clad is formed by solvent evaporated method at the Surface coating material of lithium-rich manganese base material:
Using the nitrate of zirconium and deionized water as the zirconium nitrate solution of preparation of raw material 2mol/L, weigh appropriate pure phase lithium-rich anode material Li1.2Mn0.54Ni0.13Co0.13O2, adopt mechanical agitation and ultrasonic disperse and method it is distributed in zirconium nitrate solution uniformly, controlling solid content is 50%, and under agitation as appropriate intensity, maintenance system temperature, at 90 DEG C, is uniformly coated with one layer of zirconium nitrate by solvent evaporation at substrate material surface；
(2) within 5 hours, heat treatment is carried out with 700 DEG C of calcinings, realize part lithium ion in lithium-rich manganese base material by Technology for Heating Processing to deviate to enter clad in advance, react generation lithium-containing compound with the material in clad, being formed bulk phase-doped in section transitions metallic element entrance lithium-rich manganese base material in clad, " multiple-linkage " that finally give bulk phase-doped/Surface coating/pre-de-lithium is material modified simultaneously。
After before modified, the chemical property of positive electrode is tested by button cell。According to active substance: PVDF: acetylene black=8: 1: 1 (mass ratio) weighs smear, and test electrode is the disk that diameter is about 14mm。Carrying out various electrochemical property test after the battery standing 12h assembled again, charging/discharging voltage is between 2.5-4.6V。
The SEM figure of the modified lithium-rich anode material of the multiple linkage prepared, as shown in Figure 1。By figure it can be seen that multiple linkage modified lithium-rich manganese base material surface primary particle profile becomes unintelligible, this also demonstrates that material surface has uniformly been coated with layer of substance and has defined surface coating modification。The XRD figure spectrum of the modified lithium-rich anode material of multiple linkage occurs in that Li2ZrO3Diffraction maximum, as in figure 2 it is shown, this also demonstrates that the part lithium ion in matrix lithium-rich anode material is deviate to enter clad in advance and formed pre-de-lithium and modifiy。By be fitted calculating to XRD figure spectrum obtain Multiple Join dynamic before modified after the cell parameter of lithium-rich manganese base material, as shown in table 1, lattice parameter a value fromIt is gradually increased to 2.8815 (cell parameter a value is for representing metal ion and cationic average distance), it can be seen that, in clad, part Zr element enters into lithium-rich manganese base material crystals and defines bulk phase-doped。The first charge-discharge curve chart of lithium-rich manganese base material after multiple linkage before modified, as it is shown on figure 3, when first charge-discharge electric current is 12.5mAg-1Time, the coulombic efficiency first of lithium-rich manganese base material is 71.3% before modified, and the modified lithium-rich anode material coulombic efficiency first of multiple linkage has brought up to 91.2%。After multiple linkage before modified, lithium-rich manganese base material is at 250mAg-1The cycle performance comparison diagram of current charge-discharge electricity, as shown in Figure 4, lithium-rich manganese base material capability retention after circulation 100 times is 49% before modified, and the stable circulation performance of the modified lithium-rich manganese base material of multiple linkage is significantly improved, and after circulating 100 times, capability retention is up to 92%。
Table 1: the cell parameter of lithium-rich anode material after the multiple linkage before modified that embodiment 1 prepares。
Embodiment 2
The method of modifying of the lithium-rich manganese base material that a kind of multiple linkage is modified, concretely comprises the following steps:
(1) clad is formed by spray drying method at the Surface coating material of lithium-rich manganese base material:
Using magnesium nitrate, aluminum nitrate, deionized water and ethanol as raw material, the mol ratio of magnesium elements and aluminium element controls 1: 1, the volume ratio of deionized water and ethanol is 3: 1, prepares the solution that total concentration of metal ions is 0.5mol/L, weighs appropriate pure phase lithium-rich anode material Li1.2Mn0.4Ni0.4O2, adopt mechanical agitation and ultrasonic disperse and method it is distributed to uniformly in described solution, with polyacrylamide (molecular weight about 10,000,000, anionic) for dispersant, dispersant dosage is Li1.2Mn0.4Ni0.4O210%), control solid content be 5%, then mixture is obtained after 150 DEG C of spray drying the lithium-rich anode material of Surface coating magnesium aluminum compounds；
(2) it is warming up to 800 DEG C of calcinings again after calcining 5 hours with 400 DEG C and carries out heat treatment in 2 hours, realize part lithium ion in lithium-rich manganese base material by Technology for Heating Processing to deviate to enter clad in advance, react generation lithium-containing compound with the material in clad, being formed bulk phase-doped in section transitions metallic element entrance lithium-rich manganese base material in clad, " multiple-linkage " that finally give bulk phase-doped/Surface coating/pre-de-lithium is material modified simultaneously。
The chemical property of the modified lithium-rich manganese base material of multiple linkage is tested by button cell。According to active substance: PVDF: acetylene black=8: 1: 1 (mass ratio) weighs smear, and test electrode is the disk that diameter is about 14mm。Carrying out various electrochemical property test after the battery standing 12h assembled again, charging/discharging voltage is between 2.5-4.6V。At 12.5mAg-1First charge-discharge flow down, coulombic efficiency is 96% first。At 250mAg-1, discharge capacity 189mAhg-1, after 100 times circulate, capacity retention is 99%。
Embodiment 3
The method of modifying of the lithium-rich manganese base material that a kind of multiple linkage is modified, concretely comprises the following steps:
(1) clad is formed by spray pyrolysis at the Surface coating material of lithium-rich manganese base material:
Using zinc chloride, aluminum nitrate, zirconium nitrate and ethanol as raw material, the mol ratio of zinc, aluminum and zr element controls 2: 1: 1, prepares the solution that total concentration of metal ions is 0.6mol/L, weighs appropriate pure phase lithium-rich anode material Li1.2Mn0.5Ni0.2Co0.1O2, adopt mechanical agitation and ultrasonic disperse and method it is distributed to uniformly in described solution, with polyacrylamide (molecular weight for about 7,000,000, cationic) for dispersant, dispersant dosage is Li1.2Mn0.5Ni0.2Co0.1O26%), control solid content be 15%, then mixture is obtained after 650 DEG C of spray pyrolysis the lithium-rich anode material of Surface coating zinc-aluminium zirconium compounds；
(2) it is warming up to 600 DEG C after calcining 3 hours with 500 DEG C to calcine 2 hours, finally it is warming up to 800 DEG C of calcinings and carries out heat treatment in 3 hours, realize part lithium ion in lithium-rich manganese base material by Technology for Heating Processing to deviate to enter clad in advance, react generation lithium-containing compound with the material in clad, being formed bulk phase-doped in section transitions metallic element entrance lithium-rich manganese base material in clad, " multiple-linkage " that finally give bulk phase-doped/Surface coating/pre-de-lithium is material modified simultaneously。
The chemical property of the modified lithium-rich manganese base material of multiple linkage is tested by button cell。According to active substance: PVDF: acetylene black=8: 1: 1 (mass ratio) weighs smear, and test electrode is the disk that diameter is about 14mm。Carrying out various electrochemical property test after the battery standing 12h assembled again, charging/discharging voltage is between 2.5-4.6V。At 12.5mAg-1First charge-discharge flow down, coulombic efficiency is 98% first。At 250mAg-1, discharge capacity 200mAhg-1, after 100 times circulate, capacity retention is 98%。
Claims (10)
1. the method for modifying of the lithium-rich manganese base material that a multiple linkage is modified, it is characterized in that, including: the Surface coating material in lithium-rich manganese base material forms clad, containing transition metal in described material, realize part lithium ion in lithium-rich manganese base material by Technology for Heating Processing to deviate to enter clad in advance, react generation lithium-containing compound with the material in clad, section transitions metallic element entrance lithium-rich manganese base material in clad is formed bulk phase-doped simultaneously, " multiple-linkage " that finally give bulk phase-doped/Surface coating/pre-de-lithium is material modified。
2. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 1 is modified, it is characterised in that the molecular formula of described lithium-rich manganese base material is Li1+x[NiaCobMn(1-a-b)]1-xO2, in formula, 0.1 < x < 1,0≤a < 1,0≤b < 1,0 < a+b < 1。
3. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 1 is modified, it is characterized in that, it is solvent evaporated method, hydro-thermal method, magnetron sputtering method, vapour deposition process, coprecipitation, sol-gal process, spray drying method or spray pyrolysis that the described Surface coating material in lithium-rich manganese base material forms the method for clad。
4. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 3 is modified, it is characterized in that, described solvent evaporated method includes: the preparation solution containing transition metal, lithium-rich manganese base material is distributed in the solution that above-mentioned configuration is good, control appropriate solids content, under agitation, maintenance system temperature, at 40-100 DEG C, forms clad by solvent evaporation at lithium-rich manganese base material Surface coating material。
5. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 1 is modified, it is characterised in that the described material in clad is more than one in the salt of transition metal, oxide, hydroxide and amorphous amorphous substance。
6. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 1 is modified, it is characterised in that containing more than one transition metals in the described material in clad。
7. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 1 is modified, it is characterised in that the described material in clad and the mass ratio of lithium-rich manganese base material are between 3: 1 to 1: 100。
8. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 1 is modified, it is characterised in that described Technology for Heating Processing is multistage temperature control calcining。
9. the method for modifying of the lithium-rich manganese base material that multiple linkage as claimed in claim 7 is modified, it is characterised in that described Technology for Heating Processing includes first calcining 2～65 hours at 200 DEG C～700 DEG C, then calcines 1～80 hour at 300 DEG C～1000 DEG C。
10. the lithium-rich manganese base material that the multiple linkage that the method for modifying of the lithium-rich manganese base material that the multiple linkage according to any one of claim 1-9 modifiies prepares modifiies。
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| CN106803586A (en) * | 2017-03-01 | 2017-06-06 | 深圳市贝特瑞纳米科技有限公司 | A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole |
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Application publication date: 20160622 |