CN109546126A - A kind of transition metal element doped carbon coating lithium titanate, preparation method and application - Google Patents

A kind of transition metal element doped carbon coating lithium titanate, preparation method and application Download PDF

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CN109546126A
CN109546126A CN201811428208.8A CN201811428208A CN109546126A CN 109546126 A CN109546126 A CN 109546126A CN 201811428208 A CN201811428208 A CN 201811428208A CN 109546126 A CN109546126 A CN 109546126A
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transition metal
preparation
metal element
solution
lithium titanate
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韩庆
张伟业
陈建设
李斌川
刘奎仁
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Northeastern University China
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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
    • H01M4/362—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to a kind of transition metal element doped carbon coating lithium titanates, preparation method and application.The expression formula of transition metal element doped carbon coating lithium titanate molecule is LixMpTiy‑pOz/ C, M is doping vario-property metal ion in formula, wherein 0 < x≤8,0 < p < 5,0 < y≤6,1≤z≤12,1/2≤x:y≤2.The nano-titanium dioxide and nano lithium carbonate that preparation method is the containing transition metal element for using combustion method to prepare are prepared for initial feed by high-temperature machinery force chemistry.The lithium titanate powdery material of preparation method preparation has the advantages that epigranular, quality are high, can significantly reduce synthesis temperature, and preparation process less energy consumption in preparation process, it is low to reduce production cost；The composite material battery capacity and electron conduction of acquisition are all significantly improved, and significantly improve battery performance.

Description

A kind of transition metal element doped carbon coating lithium titanate, preparation method and application
Technical field
The present invention relates to a kind of transition metal element doped carbon coating lithium titanates and its preparation method and application, belong to new Technical field of energy material preparation.
Background technique
Lithium ion battery chemical property depends primarily on electrode performance, and the selection for cathode and anode electrode material Play key effect.The lithium ion battery negative material being commercialized at present mostly uses greatly various embedding lithium carbon materials, and carbon material exists Some fatal defects, as material preparation method is more complex；Surface passivated membrane is easily formed in cyclic process, and capacity is caused to damage It loses；Meanwhile Li dendrite is easily precipitated, make battery short circuit, to cause safety problem etc..Compared with carbon negative pole material, oxide is negative Pole material specific capacity with higher, but its cycle performance is relatively poor.It is wanted therefore, it is necessary to develop and be able to satisfy multiplying power and safety The novel anode material asked.
Spinel lithium titanate (Li4Ti5O12) it because of its intrinsic characteristic is considered as in high-power lithium ion battery One of most promising negative electrode material.On the one hand, its intercalation potential with higher can prevent appearance and the solid electricity of Li dendrite The formation for solving matter interfacial film (SEI film), so that security performance is improved.On the other hand, Li4Ti5O12In lithium insertion/deintercalation Volume change is very small in journey, therefore referred to as " zero strain " material, and this " zero strain " characteristic makes it have excellent reversible Property and longer service life.Although Li4Ti5O12There is very big application potential, but Li in4Ti5O12As negative electrode of lithium ion battery Material, electric conductivity is very poor, and the current potential relative to lithium metal is higher and capacity is lower, lithium titanate battery theoretical capacity only has 175mAh/g, and electronic conductivity is lower；The production cost of another aspect lithium titanate is relatively high, limits it in society It promotes and applies.
In terms of preparation, Li is prepared4Ti5O12Main method include three kinds: solid phase method, colloidal sol-gel method and hydro-thermal method. Solid phase method is the first choice that one kind is easy to operate, is suitble to the synthetic method of large-scale industrial production and many materials synthesis Method, but the sample particle size of conventional solid-state method preparation, pattern and uniformity are all poor, largely effect on the electrification of material Learn performance；The heat treatment time of sol-gel method is longer, and temperature is higher (800-900 DEG C)；Hydro-thermal method cost is relatively high, industry Using being restricted.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of transition metal element doped carbon coating metatitanic acid The preparation method of lithium, the lithium titanate powdery material of preparation have the advantages that epigranular, quality are high, can significantly drop in preparation process Low synthesis temperature, and preparation process less energy consumption, reduce production cost；The material of preparation is applied to the lithium titanate of lithium ion battery Negative electrode material makes battery capacity and electron conduction all be significantly improved.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
A kind of transition metal element doped carbon coating lithium titanate, the expression formula of molecule are LixMpTiy-pOz/ C, M in formula For the transition metal element of doping, wherein 0 < x≤8,0 < p < 5,0 < y≤6,1≤z≤12,1/2≤x:y≤2.
Further, the M be iron (Fe), chromium (Cr), aluminium (Al), copper (Cu), zirconium (Zr), one of silver-colored (Ag) etc..
A kind of preparation method of transition metal element doped carbon coating lithium titanate comprising following steps:
S1, to TiOSO4Ammonium hydroxide is added dropwise in solution or adds urea, white flock precipitate occurs, until pH value of solution >=7, will precipitate It is washed and is filtered repeatedly with water, until without SO in filtrate4 2-Until；
S2, the precipitating that step S1 is obtained is mixed with the nitrate of transition metal, obtains transition metal with acid heating for dissolving The TiO of ion doping2+Solution；
S3, into solution, the carbonaceous organic materials solution such as addition citric acid, glucose, long chain alkane or benzene uses ammonium hydroxide later Or urea adjusts pH value of solution >=5；
S4, the solution for obtaining step S3 carry out constant temperature calcining, obtain transition metal element doped TiO2；
S5, the transition metal element doped TiO by acquisition2Nano lithium carbonate and glucose is added, stirs and evenly mixs, It is added in ball grinder；
S6, mill ball is added, vacuumized later, be passed through protective gas, start ball grinder, isothermal holding after heating；It Transition element doped carbon coating lithium titanate powder is obtained afterwards.
Preparation method as described above, it is preferable that in step s 2, the transition metal member in the transition metal nitrate Element is iron (Fe), chromium (Cr), aluminium (Al), copper (Cu), zirconium (Zr), one of silver-colored (Ag) etc..
Preparation method as described above, it is preferable that in step s 2, in the Ti and transition metal nitrate in the precipitating Dosage according to the molar ratio range of doped metallic elements and Ti be 0~0.1:1 carry out.
Preferably, the molar ratio range of doped metallic elements and Ti are 0.05~0.1:1.
Further, in step s 2, acid can use sulfuric acid or nitric acid, and when with nitric acid, what is obtained is transition metal ions Titanyl nitrate (TiO (the NO of doping3)2)。
Preparation method as described above, it is preferable that in step s3, the additional amount and TiO of the citric acid2+Molar ratio 1~30:9.
Preparation method as described above, it is preferable that in step s 4, the temperature of the constant temperature calcining is 150~1000 DEG C, Time is 2~12h.
Preparation method as described above, it is preferable that in step s 5, the transition metal element doped TiO2With nanometer Lithium carbonate is that 0.80~0.90:1 carries out ingredient according to elemental lithium and titanium elements molar ratio.
Further, the addition content of institute's glucose is scaled Li by reactant4Ti5O12C atom in molecule and glucose Molar ratio is that 100:0~20 are added.
Preferably, Li4Ti5O12The molar ratio of C atom is 100:2~20 in molecule and glucose.
That is raw material used in the present invention is really by the molar ratio range of doped metallic elements M and Ti and Li What 0~0.1:1:0.8~0.9 was added.
Preparation method as described above, it is preferable that in step s 6, the temperature of the ball grinder is preferably 200~700 DEG C, the time is 2~36h.
It uses two steps in the present invention to calcine, first step calcining is calcined in common Muffle furnace, and being formed has doping Titanium dioxide, 150~1000 DEG C of temperature range, 2~12h of time；Second step calcining, is the titanium dioxide and carbonic acid that will have been adulterated Lithium is calcined in high energy ball milling machine in ball milling, 200~700 DEG C of preferable temperature, keeps the temperature 2~36h.
Wherein, second step calcining be lithium titanate forming process, the temperature that existing ordinary skill prepares lithium titanate be 1000 DEG C or more, and used in the present invention be high temperature energy ball grinder, by ball milling make reaction temperature be reduced to 800 DEG C with Under, most preferably 400~700 DEG C are optimal reaction interval.
Preparation method as described above, it is preferable that in step s 6, additional amount and the material quality ratio of the mill ball are 15~30:1；The protective gas is inert gas, and inert gas includes argon gas.
Preparation method as described above, the molecule of the transition metal element doped carbon coating lithium titanate material finally obtained Formula is specially LixMpTiy-p Oz/C, and M is doping vario-property metal ion in formula, wherein 0 < x≤8,0 < p < 5,0 < y≤6,1 ≤ z≤12,1/2≤x:y≤2.
It is Li for pure lithium titanate molecular formula4Ti5O12, it is face-centerd cubic structure, a series of its excellent electricity Chemical property is all derived from this, improves its chemical property by containing transition metal in the present invention, while also there is no broken Badly its this structure, promotes the performance of material further.
The transition metal that transition metal element doped carbon coating lithium titanate material or preparation method as described above obtain Application of the carbon coating lithium titanate material of element doping in the negative electrode material for preparing lithium battery.
(3) beneficial effect
The beneficial effects of the present invention are:
The preparation method of transition metal element doped carbon coating lithium titanate material provided by the invention, by this method system Standby to go out to be applied to the lithium titanate composite material of lithium ion battery, battery capacity and electron conduction are all significantly improved.And it should The lithium titanate powdery material of preparation method preparation has the advantages that epigranular, quality are high, can significantly reduce conjunction in preparation process At temperature, and preparation process less energy consumption, it is low to reduce production cost.
The nano-titanium dioxide and nano lithium carbonate for the admixture transition metal element that the present invention uses combustion method to prepare are first Beginning raw material is prepared into the carbon coating lithium titanate of metallic element doping, the lithium titanate composite material by high-temperature machinery force chemistry Significantly improve battery performance.
Preparation method of the invention reduces the temperature of synthesis lithium titanate during the preparation process, and conventional solid-state method temperature is 800~1000 DEG C of synthesis, this method may synthesize at 200~700 DEG C, effectively save energy consumption, reduce cost；Preparation process In, calcining and ball milling are carried out simultaneously in same high temperature furnace, reduces operating procedure, saves the production time, be extensive Industrialized production provides new method；The lithium titanate material particle of method synthesis of the invention is uniform, and stability is good, quality It is high.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrum that sample is obtained in embodiment 1；
Fig. 2 is that the embodiment of the present invention prepares the battery of (curve 2) and the charge-discharge performance of pure lithium titanate (curve 1) battery Comparison diagram；
The scanning electron microscope (SEM) photograph of sample is obtained in Fig. 3 embodiment of the present invention 1.
Specific embodiment
The principle of the method for the present invention: the present invention is with TiOSO4For raw material, organic matter is incendiary agent, and organic matter includes lemon Acid, glucose, long chain alkane or benzene etc., and it is doped with transition metal, synthesize transient metal doped nano-TiO2.It crosses herein Strong redox reaction occurs for Cheng Zhong, the nitrate as oxidant and the organic matter as reducing agent, and burning generates big The gas of amount, can get that particle is tiny, powder of high-specific surface area.In the reaction, if excessive organic matter, which is added, is added meeting Temperature is excessively high when making to burn, and causes the crystalline form of nano-titanium dioxide to change, is changed into crystalline substance by more active Detitanium-ore-type Red stone-type is unfavorable for being synthetically prepared for the lithium titanate in later period；Burning can be made to be not enough if too low organic matter addition is added, The crystallinity of nano-titanium dioxide is bad, and burning gap is not flourishing enough, and might have the residual of the acid groups such as nitrate anion.Therefore have The additional amount and TiO (NO of machine object such as citric acid3)2Molar ratio be preferably 1~30:9.Further, when organic matter is glucose When, additional amount and TiO (NO3)2Molar ratio be preferably 1~15:9.
In the reaction process of high-temperature machinery force chemistry, reaction pressure is constant, and the mechanical force of ball milling keeps powder further thin Change and disperse more uniform, reactant is continuously available refinement, simultaneously because continual ball milling makes unreacted reaction Object surface is exposed in time, transition metal element doped TiO2It is easier to contact to be reacted with nano lithium carbonate, in this way Keep reaction more abundant, performance is more stable, and chemical property is relatively good.In addition, ball milling appropriate has refined crystal grain, has increased Specific surface area makes just to will do it to obtain more complete reaction at high temperature originally, in lower temperature so as to improve dynamic conditions Also can be realized under degree, due to the presence of ball milling, reduce the generation of agglomeration, the reactant particle uniformity made compared with It is good.The excessively high crystal shape that will lead to of ball milling temperature changes, and crossing low reaction can be insufficient, thus ball milling temperature be preferably 200~ 700 DEG C, soaking time: 2~36h.
In order to preferably explain the present invention, in order to understand, below by specific embodiment, present invention work is retouched in detail It states.
A kind of preparation method of transition metal element doped carbon coating lithium titanate, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, dropwise addition concentrated ammonia liquor or urea into solution, in solution There is white flock precipitate, adjusts pH value of solution >=7, precipitating in the pasty state, filtering is washed with deionized water, directly by solution repeatedly at this time Into filtrate without SO4 2-Until.
(2) precipitating is placed in clean beaker, and the nitrate of a certain amount of transition metal M, doping metals are added into beaker Element M/Ti molar ratio range is 0~0.1:1, with dilute HNO3Heating for dissolving obtains transition element doped TiO (NO3)2It is molten Liquid.
(3) a certain amount of carbonaceous organic material solution, such as citric acid, glucose, long chain alkane or benzene are added into solution, Optimization citric acid, additional amount and TiO (NO3)21~30:9 of molar ratio, with ammonium hydroxide adjust pH value of solution >=5.
Further, when glucose was added, additional amount and TiO (NO3)21~15:9 of molar ratio.
(4) the above solution is poured into crucible and is put into shaft furnace, 2~12h of constant temperature calcining, obtains at 150~1000 DEG C Transition metal element doped TiO2；
(5) transition metal element doped TiO will be obtained2It is raw material with nano lithium carbonate, according to elemental lithium and titanium elements Molar ratio is that 0.80~0.90:1 carries out ingredient, and the glucose of certain mass, the quality of reactant and the quality of glucose is added Than for 100:0~20；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to 15~30:1 of ratio of grinding media to material, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 2~5 times repeatedly；
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 200~700 DEG C, keep the temperature 2~36h；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, lithium titanate composite material can be obtained, according to mixing Miscellaneous ratio, the molecular formula of acquisition are specially LixMpTiy-p Oz/ C, M is doping vario-property metal ion in formula, wherein 0 x≤8 <, 0 < p < 5,0 < y≤6,1≤z≤12,1/2≤x:y≤2.
Embodiment 1
A kind of preparation method of the carbon coating lithium titanate of ferrous metal element doping, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, and concentrated ammonia liquor is added dropwise into solution, occurs in solution white Color flocculent deposit adjusts pH value of solution >=7, and precipitating in the pasty state, filtering is washed with deionized water by solution repeatedly at this time, until filtrate Middle no SO4 2-Until.
(2) precipitating is placed in clean beaker, and a certain amount of ferric nitrate is added into beaker, adulterates ferro element/Ti mole Than being 0.05:1, with dilute HNO3It dissolves by heating and obtains the TiO (NO of ferro element doping3)2Solution.
(3) a certain amount of citric acid is added into solution, makes the additional amount and TiO (NO of citric acid3)2Molar ratio 20:9, use Ammonium hydroxide adjusts pH value of solution >=5.
(4) the above solution is poured into crucible and is put into Muffle furnace, in 400 degrees Celsius of lower constant temperature calcining 3h, obtain iron The TiO of element doping2。
(5) TiO of ferrous metal element doping will be obtained2It is raw material with nano lithium carbonate, rubs according to elemental lithium and titanium elements Your ratio is that 0.85:1 carries out ingredient, the glucose of certain mass is added, the quality of reactant and the mass ratio of glucose are 100: 16；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to ratio of grinding media to material 15:1, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 3 times repeatedly；
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 700 DEG C, keep the temperature 10h；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, the carbon coating lithium titanate that Fe2O3 doping can be obtained is multiple Condensation material.Carry out X-ray measurement to sample is obtained in the embodiment obtains X-ray diffraction spectrum as shown in Figure 1, its molecular formula For Li4Fe0.25Ti4.7O12。
Embodiment 2
A kind of preparation method of the carbon coating lithium titanate of aluminum metal element doping, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, and concentrated ammonia liquor is added dropwise into solution, occurs in solution white Color flocculent deposit adjusts pH value of solution >=7, and precipitating in the pasty state, filtering is washed with deionized water by solution repeatedly at this time, until filtrate Middle no SO4 2-Until.
(2) precipitating is placed in clean beaker, and a certain amount of aluminum nitrate, doping aluminium element and Ti molar ratio are added into beaker It is 0.09:1, with dilute HNO3It dissolves by heating and obtains the TiO (NO of aluminium element doping3)2Solution.
(3) a certain amount of glucose solution, the additional amount and TiO (NO of glucose are added into solution3)2Molar ratio 10:9, PH value of solution >=5 are adjusted with urea liquid.
(4) the above solution is poured into crucible and is put into Muffle furnace, in 600 degrees Celsius of lower constant temperature calcining 4h, obtain aluminium The TiO of metallic element doping2。
(5) TiO of aluminum metal element doping will be obtained2It is raw material with nano lithium carbonate, rubs according to elemental lithium and titanium elements Your ratio is that 0.89:1 carries out ingredient, the glucose of certain mass is added, the quality of reactant and the mass ratio of glucose are 100: 20；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to ratio of grinding media to material 25:1, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 2 times repeatedly；
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 600 DEG C, keep the temperature 20h；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, the carbon coating lithium titanate that aluminium doping can be obtained is multiple Condensation material, molecular formula Li4Al0.45Ti4.5O12/C。
Embodiment 3
A kind of preparation method of the carbon coating lithium titanate of copper metal element doping, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, and concentrated ammonia liquor is added dropwise into solution, occurs in solution white Color flocculent deposit adjusts pH value of solution >=7, and precipitating in the pasty state, filtering is washed with deionized water by solution repeatedly at this time, until filtrate Middle no SO4 2-Until.
(2) precipitating is placed in clean beaker, and a certain amount of copper nitrate is added into beaker, adulterates copper/Ti mole Than being 0.1:1, with dilute HNO3It dissolves by heating and obtains the TiO (NO of copper doping3)2Solution.
(3) a certain amount of citric acid solution, the additional amount and TiO (NO of citric acid are added into solution3)2Molar ratio 15:9, PH value of solution >=5 are adjusted with urea liquid.
(4) the above solution is poured into crucible and is put into Muffle furnace, in 500 degrees Celsius of lower constant temperature calcining 6h, obtain copper The TiO of metallic element doping2。
(5) TiO of copper metal element doping will be obtained2It is raw material with nano lithium carbonate, rubs according to elemental lithium and titanium elements Your ratio is that 0.90:1 carries out ingredient, the glucose of certain mass is added, the quality of reactant and the mass ratio of glucose are 100: 25；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to ratio of grinding media to material 30:1, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 4 times repeatedly；
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 500 DEG C, keep the temperature 36h；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, the carbon coating lithium titanate that Copper-cladding Aluminum Bar can be obtained is multiple Condensation material, molecular formula Li4Cu0.5Ti4.5O12/C。
Embodiment 4
A kind of preparation method of the carbon coating lithium titanate of silver metal element doping, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, and concentrated ammonia liquor is added dropwise into solution, occurs in solution white Color flocculent deposit adjusts pH value of solution >=7, and precipitating in the pasty state, filtering is washed with deionized water by solution repeatedly at this time, until filtrate Middle no SO4 2-Until.
(2) precipitating is placed in clean beaker, and a certain amount of silver nitrate is added into beaker, adulterates silver element/Ti mole Than being 0.04:1, with dilute HNO3It dissolves by heating and obtains the TiO (NO of silver element doping3)2Solution.
(3) a certain amount of citric acid solution, the additional amount and TiO (NO of citric acid are added into solution3)2Molar ratio 10:9, PH value of solution >=5 are adjusted with urea liquid.
(4) the above solution is poured into crucible and is put into Muffle furnace, in 400 degrees Celsius of lower constant temperature calcining 12h, obtain silver The TiO of metallic element doping2。
(5) TiO of silver metal element doping will be obtained2It is raw material with nano lithium carbonate, rubs according to elemental lithium and titanium elements Your ratio is that 0.82:1 carries out ingredient, the glucose of certain mass is added, the quality of reactant and the mass ratio of glucose are 100: 10；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to ratio of grinding media to material 30:1, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 3 times repeatedly；
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 650 DEG C, keep the temperature 36h；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, the carbon coating lithium titanate that Ag doping can be obtained is multiple Condensation material, molecular formula Li4Ag0.2Ti4.8O12/C。
Embodiment 5
A kind of preparation method of the carbon coating lithium titanate of zirconium metallic element doping, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, and concentrated ammonia liquor is added dropwise into solution, occurs in solution white Color flocculent deposit adjusts pH value of solution >=7, and precipitating in the pasty state, filtering is washed with deionized water by solution repeatedly at this time, until filtrate Middle no SO2 4-Until.
(2) precipitating is placed in clean beaker, and a certain amount of zirconium nitrate is added into beaker, adulterates zr element/Ti mole Than being 0.07:1, with dilute HNO3It dissolves by heating and obtains the TiO (NO of zr element doping3)2Solution.
(3) a certain amount of citric acid solution, the additional amount and TiO (NO of citric acid are added into solution3)2Molar ratio 15:9, PH value of solution >=5 are adjusted with urea liquid.
(4) the above solution is poured into crucible and is put into Muffle furnace, in 1000 degrees Celsius of lower constant temperature calcining 2h, obtain zirconium The TiO of metallic element doping2。
(5) TiO of zirconium metallic element doping will be obtained2It is raw material with nano lithium carbonate, rubs according to elemental lithium and titanium elements Your ratio is that 0.86:1 carries out ingredient, the glucose of certain mass is added, the quality of reactant and the mass ratio of glucose are 100: 5；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to ratio of grinding media to material 30:1, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 3 times repeatedly
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 600 DEG C, heat preservation is for 24 hours；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, the carbon coating lithium titanate that zirconium doping can be obtained is multiple Condensation material, molecular formula Li4Zr0.35Ti4.6O12/C。
Embodiment 6
A kind of preparation method of the carbon coating lithium titanate of chromium metallic element doping, includes the following steps:
(1) a certain amount of TiOSO is weighed4Solid adds water to dissolve by heating, and urea is added into solution, occurs white wadding in solution Shape precipitating, adjusts pH value of solution >=7, and precipitating in the pasty state, filtering is washed with deionized water by solution repeatedly at this time, until nothing in filtrate SO4 2-Until.
(2) precipitating is placed in clean beaker, and a certain amount of chromic nitrate is added into beaker, and doping chromium/Ti/Li rubs Your ratio is 0.06:1, with dilute HNO3It dissolves by heating and obtains the TiO (NO of chromium doping3)2Solution.
(3) a certain amount of citric acid solution, the additional amount and TiO (NO of citric acid are added into solution3)2Molar ratio 20:9, PH value of solution >=5 are adjusted with urea liquid.
(4) the above solution is poured into crucible and is put into Muffle furnace, in 700 degrees Celsius of lower constant temperature calcining 3h, obtain chromium The TiO of metallic element doping2。
(5) TiO of chromium metallic element doping will be obtained2It is raw material with nano lithium carbonate, rubs according to elemental lithium and titanium elements Your ratio is that 0.86:1 carries out ingredient, the glucose of certain mass is added, the quality of reactant and the mass ratio of glucose are 100: 15；Prior stirring pretreatment is carried out, material is uniformly mixed, then, is fitted into ball grinder；
(6) mill ball is added according to ratio of grinding media to material 20:1, closes the lid, seal ball grinder；
(7) ball grinder is put into high temperature energy ball grinder burner hearth, first carries out vacuumize process, then be passed through argon gas protection Gas, 3 times repeatedly
(8) start ball mill, it is lasting to rotate, while burner hearth is warming up to 700 DEG C, keep the temperature 36h；
(9) it closes ball mill and waits for that burner hearth is cooled to room temperature, take out ball grinder, the carbon coating lithium titanate that Cr doping can be obtained is multiple Condensation material, molecular formula Li4Cr0.3Ti5O12/C。
Using the transition metal element doped carbon coating lithium titanate composite material of above-described embodiment method preparation for making When standby battery cathode, the chemical property of battery is substantially increased, under equal conditions, using transition metal prepared by the present invention The carbon coating lithium titanate composite material of element doping has 10% using the specific capacity raising that pure ground lithium titanate prepares battery than individually More than.Such as with using embodiment 1 prepare Li4Fe0.25Ti4.7O12/ C, as cathode, the battery of preparation compares after measured Capacity reaches 195mAh/g (as shown in Fig. 2, No. 2 curves in corresponding diagram 2), and uses the lithium titanate battery specific capacity of pure phase only 175mAh/g (No. 1 curve in corresponding diagram 2) can be reached.
Of the transition metal element doped carbon coating lithium titanate composite material of preparation method preparation provided by the invention Highly uniform, the granularity very little of grain, meets the requirement for doing lithium ion battery negative material, enumerates sweeping for the material of the preparation of embodiment 1 Retouch electron microscope it is as shown in Figure 3 for illustrate that particle is uniform, granularity is small.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint What those skilled in the art can use the equivalence enforcement that technology contents disclosed above were changed or be modified as equivalent variations Example.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to the above embodiments What simple modification, equivalent variations and remodeling, still falls within the protection scope of technical solution of the present invention.

Claims (10)

1. a kind of transition metal element doped carbon coating lithium titanate, which is characterized in that the expression formula of its molecule is LixMpTiy- pOz/ C, M is the transition metal element of doping in formula, wherein 0 < x≤8,0 < p < 5,0 < y≤6,1≤z≤12,1/2≤x:y ≤ 2, the M are iron, chromium, aluminium, copper, zirconium or silver.
2. a kind of preparation method of transition metal element doped carbon coating lithium titanate comprising following steps:
S1, to TiOSO4Ammonium hydroxide is added dropwise in solution or adds urea, white flock precipitate occurs, until pH value of solution >=7, will precipitate repeatedly Filtering, until without SO in filtrate4 2-Until；
S2, the precipitating that step S1 is obtained is mixed with the nitrate of transition metal, obtains transition metal ions with acid heating for dissolving The TiO of doping2+Solution；
S3, the carbonaceous organic material that citric acid, glucose, long chain alkane or benzene are added into solution, later, with ammonium hydroxide or urea Adjust pH value of solution >=5；
S4, the solution for obtaining step S3 carry out constant temperature calcining, obtain transition metal element doped TiO2；
S5, the transition metal element doped TiO by acquisition2Nano lithium carbonate and glucose is added, stirs and evenly mixs, is added In ball grinder；
S6, mill ball is added, vacuumized later, be passed through protective gas, start ball grinder, isothermal holding after heating；It obtains later Obtain transition element doped carbon coating lithium titanate powder.
3. preparation method as claimed in claim 2, which is characterized in that in step s 2, in the transition metal nitrate Transition metal element is any one of iron, chromium, aluminium, copper, zirconium or silver；In Ti and transition metal nitrate in the precipitating Dosage is that 0~0.1:1 is carried out according to the molar ratio range of doped metallic elements and Ti.
4. preparation method as claimed in claim 2, which is characterized in that in step s3, the additional amount and TiO of the citric acid2 +1~30:9 of molar ratio.
5. preparation method as claimed in claim 2, which is characterized in that in step s 4, the temperature of the constant temperature calcining is 150 ~1000 DEG C, the time is 2~12h.
6. preparation method as claimed in claim 2, which is characterized in that in step s 5, described transition metal element doped TiO2Ingredient is carried out for 0.80~0.90:1 according to elemental lithium and titanium elements molar ratio with nano lithium carbonate.
7. preparation method as claimed in claim 2, which is characterized in that in step s 5, the addition content of institute's glucose is by reaction Object is scaled Li4Ti5O12The molar ratio of molecule and C atom in glucose is that 100:0~20 are added.
8. preparation method as claimed in claim 2, which is characterized in that in step s 6, the temperature of the ball grinder is preferably 200~700 DEG C, the time is 2~36h.
9. preparation method as claimed in claim 2, which is characterized in that in step s 6, the additional amount and original of the mill ball Material mass ratio is 15~30:1；The protective gas is inert gas.
10. any in transition metal element doped carbon coating lithium titanate material or claim 2-9 described in claim 1 The transition metal element doped carbon coating lithium titanate material that one preparation method obtains is in the negative electrode material for preparing lithium battery Application.
CN201811428208.8A 2018-11-27 2018-11-27 A kind of transition metal element doped carbon coating lithium titanate, preparation method and application Pending CN109546126A (en)

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CN110078180A (en) * 2019-05-22 2019-08-02 东北大学 A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid
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Application publication date: 20190329