CN109449433A - A kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material - Google Patents

A kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material Download PDF

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CN109449433A
CN109449433A CN201811287214.6A CN201811287214A CN109449433A CN 109449433 A CN109449433 A CN 109449433A CN 201811287214 A CN201811287214 A CN 201811287214A CN 109449433 A CN109449433 A CN 109449433A
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negative electrode
electrode material
lithium titanate
doped
earth
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秦蒙
李东剑
李军飞
李悦明
赵少怀
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Thornton New Energy Technology (Changsha) Co.,Ltd.
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Soundon New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of preparation methods of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material, comprising: 1) by the LiOHH of 0.008~0.012mol2O, the MCl37H of the butyl titanate of 2~4ml and 0.04~0.1mmol2O is mixed, is dispersed, being stirred for obtaining suspension, and wherein M is one of La, Ce；2) suspension is subjected to hydro-thermal reaction, is then filtered, is washed, obtain graphite-doping lithium titanate anode material presoma；3) it is dried in vacuo, is then ground to powder；4) rare earth element M doped lithium titanate nanometer sheet negative electrode material Li is obtained by the powder after grinding is thermally treated4Ti5‑xMxO12.Method and process of the invention is simple, does not need pre-burning and gas shield and easy to industrialized production；Not only yield is high for lithium titanate anode material obtained, but also still has excellent volumetric properties, cycle performance and high rate performance under high current density.

Description

A kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material
Technical field
The present invention relates to a kind of preparation methods of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material.
Background technique
Along with the fast development of current electric car, people's urgent need is used with excellent electrochemical performance and height Dynamical system of the trustworthy battery of safety as electric car.And currently used LiCoO2- graphite battery System is since the graphite for using intercalation potential very low is as cathode, to easily generate Li dendrite in graphite surface and then puncture battery Mode separation strapping carrys out security risk.For this purpose, lithium titanate is widely studied with its own plurality of advantages.
Lithium titanate is compared to conventional graphite as a kind of lithium cell cathode material, and possessed advantage has: (1) discharging Voltage platform height (1.55vs Li/Li+) it is much higher than the intercalation potential of graphite, so that the formation of dendrite lithium is fundamentally inhibited, And it does not react with electrolyte；(2) lithium titanate anode material is referred to as that " zero answers in charge and discharge process without volume change Become material ", greatly improve itself cycle performance and security performance.But electronic conductivity and Li that lithium titanate itself is low+Diffusion coefficient seriously limits multiplying power and cycle performance of the lithium titanate anode material under high current density.It is vast in recent years Researcher takes numerous methods such as Heteroatom doping and highly conductive dose of cladding is waited measures to go to improve the electronics electricity of lithium titanate Conductance and Li+Diffusion coefficient, although can satisfy the multiplying power of lithium titanate anode material and cycle performance demand under conventional multiplying power, It is to show that its multiplying power and cycle performance are undesirable by investigating relative literature in high current density such as 5A/g or more.
Currently, commonplace method is to prepare lithium titanate anode material using hydro-thermal method, such as the patent Shen of wangdan et al. First with metatitanic acid ester hydrolysis in polyethylene glycol (PEG) and the mixed solution of ethyl alcohol, it please exist again later in CN103022461 A The some time is stood in the environment being connected under nitrogen atmosphere and obtains TiO 2 precursor.Then, then the presoma it is added To stirring in the mixed solution of water and ethyl alcohol, the soluble compound of lithium hydroxide and metal M is added later, using one section It is transferred in water heating kettle and reacts after time stirring.Finally the powdery product being collected into is calcined under the conditions of 300~600 DEG C 1~6h.Just obtain the lithium titanate anode material of finished product.However, there are complex process for the preparation process, caused into using nitrogen The higher and soluble compound using metal M of this and energy consumption cannot regulate and control in turn titanium ion valence state in lithium titanate lattice Improve the problems such as its conductivity.
Summary of the invention
The object of the present invention is to provide a kind of simple process, energy consumption and cost is relatively low and have high conductance and lithium from The preparation method of the rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material of sub- diffusion coefficient.
In order to achieve the above object, the present invention the following steps are included:
1) by the LiOHH of 0.008~0.012mol2O, the butyl titanate of 2~4ml and 0.04~0.1mmol MCl3·7H2O mixing, then ultrasonic disperse is allowed to uniformly, then stir under the conditions of 200~400r/min and sequentially add 15~ 25ml ethyl alcohol and 20~30ml deionized water, stirring obtain uniformly mixed suspension in 2~4 hours, and wherein M is in La, Ce It is a kind of；
2) suspension for obtaining step 1) is transferred in water heating kettle, and is heated to 150~180 DEG C, reacts 24~48h, 23~25 DEG C are cooled to, then which is used to 40~80ml ethanol washing under conditions of suction filtration, is removed in material The remaining impurity in portion, obtains graphite-doping lithium titanate anode material presoma；
3) it by graphite-doping lithium titanate anode material presoma obtained in step 2), is dried in vacuo at 50~80 DEG C, then Grind into powder；
4) powder after grinding is warming up to 550~800 DEG C of 3~7h of heat preservation with the rate of 2~5 DEG C/min, be cooled to 23~25 DEG C, obtain rare earth element M doped lithium titanate nanometer sheet negative electrode material Li4Ti5-xMxO12。
Preferably, by the LiOHH of 0.01mol in the step 1)2O, the butyl titanate of 3ml and 0.06mmol MCl3·7H2O is made into uniform suspension.
Preferably, the volume of suspension accounts for the 70% of container volume in water heating kettle in the step 2).
Preferably, heating rate is 2 DEG C/min in the step 4).
The beneficial effects of the present invention are:
1, the present invention provides a kind of easy lithium titanate anode material method of modifying, i.e., when reacting initial by rare earth member Plain additive, that is, corresponding MCl3·7H2O crystalline hydrate, lithium hydroxide and butyl titanate are mixed into uniform solution, Zhi Houli Ultra-thin partial size has been prepared between 50~240nm under high temperature, high pressure and subsequent heat treatment condition with one step hydro thermal method Rear-earth-doped lithium titanate nanometer sheet lithium cell cathode material, which is evenly distributed, piece is relatively thin and not Inactivation of reuniting occurs.
2, due to using the method for the present invention preparation rear-earth-doped lithium titanate nanometer sheet crystal growth direction be along [110] crystal orientation not only has be conducive to Li in this way+In the three-dimensional ion channel of [110] crystal orientation transmission, and the thin nanometer sheet formed Structure is conducive to improve Li+Electrochemical reaction speed between electrode slice and electrolyte.
3, using rare earth element to Li4Ti5O12Doping, with undoped Li4Ti5O12It compares under phase same multiplying, electrochemistry Statistics indicate that: not only 30~45mAh/g can be improved in specific discharge capacity, and follows after 1000 circle circulations under 5A/g current density Environmentally friendly holdup is up to 86%.
4, compared with the existing technology, method and process of the invention is simple, does not need pre-burning and gas shield and is easy to industry Metaplasia produces；Not only yield is high for lithium titanate anode material obtained, and still have under high current density excellent volumetric properties, Cycle performance and high rate performance.When current density is respectively 10A/g and 20A/g: Ce doped titanic acid lithium titanate cathode material electric discharge ratio Capacity respectively reaches 137mAh/g and 123mAh/g, and La doped titanic acid lithium titanate cathode material specific discharge capacity respectively reaches 120mAh/g And 113mAh/g.
Detailed description of the invention
Fig. 1 is the SEM image of the lithium titanate ultrathin nanometer piece negative electrode material of rare earth element cerium dopping in embodiment 1；
The SEM image of lithium titanate ultrathin nanometer piece negative electrode material of the Fig. 2 undoped with rare earth element；
Fig. 3 is that the TEM image of the lithium titanate ultra-thin titanium nanometer sheet of rare earth element cerium dopping in embodiment 1 is (wherein internal to insert Figure is corresponding selective electron diffraction figure)；
Fig. 4 be lithium titanate ultrathin nanometer piece corresponding to embodiment 1,2 and comparative example 3 0.2A/g~20A/g seven not With high rate performance curve corresponding under current density；
Fig. 5 is the lithium titanate ultrathin nanometer piece negative electrode material of rare earth element La doped in embodiment 2 in 5A/g current density Lower corresponding cycle performance curve；
The lithium titanate ultrathin nanometer piece negative electrode material of rare earth element cerium dopping is under 5A/g current density in Fig. 6 embodiment 1 Corresponding cycle performance curve.
Specific embodiment
Embodiment 1
1) by the LiOHH of 0.01mol2O, the CeCl of the butyl titanate of 3ml and 0.08mmol3·7H2O pours into beaker Ultrasound 20min keeps its evenly dispersed in inherent ultrasonic machine, later, is placed on magnetic stirring apparatus, in 350r/min condition The lower 15ml ethyl alcohol that is first added adds 20ml deionized water, and stirs 4h finally and uniformly mixed suspension can be obtained；
2) suspension being uniformly mixed in step 1 is transferred in water heating kettle, and is heated to 180 DEG C, react 48h, then cold But to 25 DEG C, then, which is used 80ml ethanol washing 3 times under conditions of suction filtration, to remove material internal residual Impurity, graphite-doping lithium titanate anode material presoma can be obtained；
3) it by graphite-doping lithium titanate anode material presoma obtained in step 2, is dried in vacuo, is then ground at 60 DEG C Powder；
4) powder after grinding is warming up to 700 DEG C of heat preservation 7h with the rate of 2 DEG C/min, is cooled to 25 DEG C, obtains dilute Earth elements cerium (Ce) doped lithium titanate nanometer sheet negative electrode material Li4Ti5-xCexO12。
Metatitanic acid from the SEM image of Fig. 1 Ce doped lithium titanate nanometer sheet negative electrode material with Fig. 2 undoped with rare earth element Rare earth doped lithium titanate nanometer sheet partial size is less than undoped known to the SEM image comparison of lithium ultrathin nanometer piece negative electrode material Lithium titanate nanometer sheet partial size, show rare earth doped there is refinement crystal particle scale and to be conducive to nanometer sheet equally distributed Effect, the compound crystal phase known to the TEM image of Fig. 3 be cubic spinel type lithium titanate phase and its be a nanometer chip architecture, This is consistent with SEM result.
Embodiment 2
1) by the LiOHH of 0.008mol2O, the LaCl of the butyl titanate of 2ml and 0.04mmol3·7H2O pours into beaker Ultrasound 30min keeps its evenly dispersed in inherent ultrasonic machine, later, is placed on magnetic stirring apparatus, in 200r/min condition The lower 25ml ethyl alcohol that is first added adds 30ml deionized water, and stirs 2h finally and uniformly mixed suspension can be obtained；
2) suspension being uniformly mixed in step 1) is transferred in water heating kettle, and is heated to 150 DEG C, reacted for 24 hours, then cold But to 23 DEG C, then, which is used 40ml ethanol washing 2 times under conditions of suction filtration, to remove material internal residual Impurity, graphite-doping lithium titanate anode material presoma can be obtained；
3) it by graphite-doping lithium titanate anode material presoma obtained in step 2), is dried in vacuo at 50 DEG C, then grinds At powder；
4) powder after grinding is warming up to 550 DEG C of heat preservation 3h with the rate of 5 DEG C/min, is cooled to 23 DEG C, obtains dilute Earth elements lanthanum (La) doped lithium titanate nanometer sheet negative electrode material Li4Ti5-xLaxO12。
Embodiment 3
1) by the LiOHH of 0.012mol2O, the CeCl of the butyl titanate of 4ml and 0.1mmol3·7H2O pours into beaker Ultrasound 25min keeps its evenly dispersed in inherent ultrasonic machine, later, is placed on magnetic stirring apparatus, in 400r/min condition The lower 20ml ethyl alcohol that is first added adds 25ml deionized water, and stirs 3h finally and uniformly mixed suspension can be obtained；
2) suspension being uniformly mixed in step 1) is transferred in water heating kettle, and is heated to 160 DEG C, react 36h, then cold But to 24 DEG C, then, which is used 60ml ethanol washing 3 times under conditions of suction filtration, to remove material internal residual Impurity, graphite-doping lithium titanate anode material presoma can be obtained；
3) it by graphite-doping lithium titanate anode material presoma obtained in step 2), is dried in vacuo at 80 DEG C, then grinds At powder；
4) powder after grinding is warming up to 800 DEG C of heat preservation 5h with the rate of 4 DEG C/min, is cooled to 24 DEG C, obtains dilute Earth elements cerium (Ce) doped lithium titanate nanometer sheet negative electrode material Li4Ti5-xCexO12。
Comparative example
The preparation of above-mentioned undoped lithium titanate ultrathin nanometer piece cathode, comprising the following steps:
1) by the LiOHH of 0.01mol2The butyl titanate of O and 3ml pours into the interior ultrasound 20min in ultrasonic machine of beaker Keep its evenly dispersed, later, be placed on magnetic stirring apparatus, 15ml ethyl alcohol is first added under the conditions of 350r/min and adds 20ml deionized water, and stir 4h finally and uniformly mixed suspension can be obtained；
2) suspension being uniformly mixed in step 1) is transferred in water heating kettle, and is heated to 180 DEG C, react 48h, then cold But to 25 DEG C, the suspension is then used into 80ml ethanol washing several times under conditions of suction filtration, to remove material internal residual Impurity, graphite-doping lithium titanate anode material presoma can be obtained；
3) it by graphite-doping lithium titanate anode material presoma obtained in step 2), is dried in vacuo at 60 DEG C, then grinds At powder；
4) powder after grinding is warming up to 700 DEG C of heat preservation 7h with the rate of 2 DEG C/min, is cooled to 25 DEG C, obtains not Doped lithium titanate nanometer sheet negative electrode material Li4Ti5O12。
Graphite-doping lithium titanate anode material in the present invention is realized by being assembled into button half-cell.Button half-cell Assembling through the following steps that realize:
1) preparation of electrode be by above-mentioned graphite-doping lithium titanate anode material, conductive black and PVDF according to mass ratio be 80: The mass ratio of 15:5 mixes, and said mixture, which is made, using mortar under conditions of using NMP as solvent uniform is had centainly The slurry of stickiness is coated on the coarse copper foil current collector face of 15um thickness, be placed on 120 DEG C of heat preservation 20h in vacuum drying oven, then It recycles roll squeezer to further increase the surface density of electrode, and guarantees falling off for inactive substance during roll-in；
2) electrode slice for pressing step 1) central roll is cut into the electrode slice of Φ 12mm using MTI hand microtome, later handle Electrode slice is transferred quickly to carry out the assembly of button cell in Braun glove box.In assembling process: the electrode slice that will have been cut As cathode, commercialization lithium piece is reference electrode, the LiPF of electrolyte commodity in use 1mol/L6, diaphragm is using Celgard public affairs 2400 type microporous polypropylene films of department.According to anode cover has first been laid flat, then anode electrode piece is carefully sandwiched just with tweezers In the shell of pole, a small amount of electrolyte is measured with pipettor later and instillation electrode slice surface is slowly put into diaphragm and makes later dropwise Electrode slice is still in diaphragm central location；Electrolyte is added dropwise again makes its complete wetting electrode slice, is then put into negative electricity with tweezers Pole piece finally assembles battery according to the order for placing gasket, elastic slice and negative electrode casing, and gently pressure reuses hand-operated battery sealing machine Battery is sealed.
Chemical property detection method when lithium titanate ultrathin nanometer plate electrode material is as button half-cell
Using button half-cell assemble method among the above, the full battery assembled is firstly the need of being stored at room temperature 2h.Later, Its multiplying power and cycle performance test are all made of constant current charge-discharge test method, i.e., precise and calculate in electrode slice active first The quality of substance calculates separately out its corresponding actual current size according to the current density of 0.2~20A/g later, further in accordance with The work step of constant-current charge, constant-current discharge and circulation, using the 2000 type battery test system of BT of ARBIN company, 1~3V's Under voltage window range, each button cell is tested for the property.Shown by test result Fig. 4: La adulterates LTO low Under current density, specific discharge capacity and undoped LTO specific capacity are close, but at high current density 5A/g, specific capacity is improved 20~50mAh/g.And the specific capacity of Ce doping LTO is under 0.2~20A/g current density, specific capacity improves 20~ 70mAh/g.Meanwhile in Fig. 5 and Fig. 6 cerium or La doped lithium titanate nanometer anode material also with BT 2000 in 5A/g electric current Under density, tested circulating battery 1000 encloses corresponding cycle performance curve.It is computed and show that the circulation conservation rate of the two is equal It is 86%, shows and introduce the rare earth doped chemical property for being conducive to improve lithium titanate anode material, especially in big electricity Under the conditions of current density.

Claims (5)

1. a kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material, characterized in that include lower step:
1) by the LiOHH of 0.008~0.012mol2O, the MCl3 of the butyl titanate of 2~4ml and 0.04~0.1mmol 7H2O mixing, then ultrasonic disperse is allowed to uniformly, then is stirred under the conditions of 200~400r/min and sequentially added 15~25ml second Pure and mild 20~30ml deionized water, stirring obtain uniformly mixed suspension in 2~4 hours, and wherein M is one of La, Ce；
2) suspension for obtaining step 1) is transferred in water heating kettle, and is heated to 150~180 DEG C, reacts 24~48h, then cold But to 23~25 DEG C, then which is used to 40~80ml ethanol washing under conditions of suction filtration, it is residual removes material internal The impurity stayed obtains graphite-doping lithium titanate anode material presoma；
3) it by graphite-doping lithium titanate anode material presoma obtained in step 2), is dried in vacuo at 50~80 DEG C, then grinds At powder；
4) powder after grinding is warming up to 550~800 DEG C of 3~7h of heat preservation with the rate of 2~5 DEG C/min, it is cooled to 23~ 25 DEG C, obtain rare earth element M doped lithium titanate nanometer sheet negative electrode material Li4Ti5-xMxO12。
2. a kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material according to claim 1, characterized in that By the LiOHH of 0.01mol in the step 1)2O, the MCl of the butyl titanate of 3ml and 0.06mmol3·7H2O is made into uniform Suspension.
3. according to claim 1 or 2 a kind of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material preparation method, it is special Sign is that the volume of suspension accounts for the 70% of container volume in water heating kettle in the step 2).
4. according to claim 1 or 2 a kind of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material preparation method, it is special Sign is that heating rate is 2 DEG C/min in the step 4).
5. a kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material according to claim 3, characterized in that Heating rate is 2 DEG C/min in the step 4).
CN201811287214.6A 2018-10-31 2018-10-31 A kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material Withdrawn CN109449433A (en)

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CN110759379A (en) * 2019-10-31 2020-02-07 湘潭大学 Preparation method and application of 0D/2D heterostructure composite negative electrode material
CN115286046A (en) * 2022-06-27 2022-11-04 广东邦普循环科技有限公司 Copper-doped lithium cobalt oxide precursor, positive electrode material, and preparation methods and applications thereof

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CN110729473A (en) * 2019-10-16 2020-01-24 桑顿新能源科技(长沙)有限公司 Preparation method of lithium titanate/copper sulfide nano compound
CN110759379A (en) * 2019-10-31 2020-02-07 湘潭大学 Preparation method and application of 0D/2D heterostructure composite negative electrode material
CN115286046A (en) * 2022-06-27 2022-11-04 广东邦普循环科技有限公司 Copper-doped lithium cobalt oxide precursor, positive electrode material, and preparation methods and applications thereof
CN115286046B (en) * 2022-06-27 2023-07-07 广东邦普循环科技有限公司 Copper-doped lithium cobalt oxide precursor, positive electrode material, preparation method and application of positive electrode material

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