CN108493427A - Micro-nano Nb for lithium ion battery electrode material2O5Raw powder's production technology - Google Patents

Micro-nano Nb for lithium ion battery electrode material2O5Raw powder's production technology Download PDF

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Publication number
CN108493427A
CN108493427A CN201810358785.8A CN201810358785A CN108493427A CN 108493427 A CN108493427 A CN 108493427A CN 201810358785 A CN201810358785 A CN 201810358785A CN 108493427 A CN108493427 A CN 108493427A
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powder
micro
nano
ion battery
lithium ion
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吕建国
陈鸿文
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention discloses a kind of hydro-thermal method method preparation Nb2O5The method of powder lithium ion battery electrode material, including:1)By NbCl5It is put into hydro-thermal reaction axe liner and absolute ethyl alcohol and distilled water stirring is added;2)Reaction ax, which is put into, carries out hydro-thermal reaction in drying box;4)Reactant is removed after the completion of reaction, is dried afterwards several times with deionized water and absolute ethyl alcohol eccentric cleaning;5)Dried powder is put into tube furnace and is calcined to obtain the final product.The present invention is easy to operate, does not need complex device, synthesized micro/nano level Nb2O5Powder is prepared by mixing into li-ion electrode materials with graphene uniform, and excellent chemical property is shown for lithium-ion battery system, 158mAh g are shown under the current density of 0.5C‑1High specific discharge capacity, under the high current of 5C after 100 cycle charge-discharges, remain to keep 90% or more specific capacitance value.

Description

Micro-nano Nb for lithium ion battery electrode material2O5Raw powder's production technology
Technical field
The present invention relates to lithium ion battery electrode material preparation more particularly to the niobide lithium ion batteries of micro nano structure Electrode material field.
Background technology
In recent years, as conventional fossil fuel is being petered out, the use of conventional fossil fuel causes environmental pollution It is valued by people, therefore the new energy and new energy storage and occupation mode are existing to solve there is an urgent need for developed Crisis.Lithium ion battery has high voltage, high power capacity, light and advantages of environment protection, has developed since nineteen ninety is commercialized Rapidly, especially in field of portable electronic devices, instead of traditional ni-Cd, Ni-MH battery, become the heat of new energy field Point.
The negative material of the lithium ion battery of commercialization at present is mainly graphite, and embedding de- lithium current potential connects very much with lithium metal Closely, it be easy to cause lithium dendrite growth and passes through diaphragm, the loss of lithium ion is not only caused to be also easy to make battery short circuit and form peace Full hidden danger.So looking for other lithium ion battery negative materials and gradually having become new energy field instead of conventional graphite material Common recognition.Wherein, niobium base oxide has high embedding de- lithium current potential(1.2~1.6V vs Li+/Li), have a safety feature and be not easy Form SEI films.There are two oxidation-reduction potentials pair for each niobium atom meeting in charge and discharge process(Nb5+/Nb4+、Nb4+/Nb3 +), this type oxide theoretical specific capacity is relatively high.In niobium base oxide, Nb2O5It is that most common most performances are best One type oxide, other oxides have not been reported substantially for lithium ion battery.Nb2O5Stratiform " shear surface ReO3 structures " can The reversible embedding de- behavior of lithium ion occurs, during which the structure of material internal does not change substantially, has good stable circulation Property;Its theoretical specific capacity is 200mAh g-1, there is excellent high rate performance.
Nanosizing material has many excellent characteristics, such as height ratio capacity, high rate capability.In the present invention, it uses Hydro-thermal method realizes Nb by controlling its reaction temperature and reaction time2O5Successful preparation and by its micro-nanoization, further The Nb of optimization2O5Chemical property.And by the Nb of micro-nanoization2O5Uniform admixed graphite alkene is as negative electrode of lithium ion battery material Material carries out electrochemical property test, finds synthesized micro-nanoization Nb2O5With good high rate performance and cyclical stability Energy.
Invention content
Niobium type oxide is lithium ion battery electrode material a kind of very excellent and with good development prospect, wherein Nb2O5As most common a kind of primary consideration of even more lithium ion battery electrode material in niobium type oxide, as one kind The exploration of the lithium ion battery electrode material of excellent properties, the present invention is directed to advanced optimize Nb2O5Performance, make its apply in It further close to theoretical specific capacity, is designed by rational material microstructure, and by simple preparation method, realizes micro-nano Rice structure Nb2O5Powder, and applied and lithium ion battery.
For achieving the above object, the technical solution adopted by the present invention is:
The present invention provides a kind of micro-nano Nb for lithium ion battery electrode material2O5Raw powder's production technology, the system Preparation Method is hydrothermal method, is included the following steps:
1)It uses deionized water and ethyl alcohol to clean hydro-thermal reaction axe liner successively, then dries;
2)Weigh a certain amount of NbCl5It is put into hydrothermal reaction kettle liner, absolute ethyl alcohol and stirring certain time is added, adds distillation Water stirs same time, forms the mixed solution of ethyl alcohol and water;
3)Liner is fitted into reaction ax, is put into drying box, certain temperature and time response are set, carries out hydro-thermal reaction;
4)After the completion of reaction, several times by reactant deionized water and absolute ethyl alcohol eccentric cleaning, it is then placed in drying box, The dry regular hour at certain temperature in air;
5)Powder after drying is put into tube furnace and is calcined, certain temperature is heated under certain heating rate, in sky The regular hour is calcined in gas to get the Nb with micro nano structure2O5Powder.
Further, the step 2)Middle mixing time is 30min, and raw material is made fully to dissolve.
Further, the step 3)Middle drying box temperature is 210 DEG C~230 DEG C, and soaking time is 20~24 hours.
Further, the step 4)Middle drying temperature is 60 DEG C, and drying time is 12 hours.
Further, the step 5)Middle tube furnace heating rate is 4 DEG C/min, is heated to 800 DEG C and calcines 2 hours.
The present invention also provides micro-nano Nb made from above-mentioned preparation method2O5Powder, it is characterised in that:The Nb2O5Powder Body, which is micron particles, about 1 μm of microns Particle size, and particle surface, has apparent micro nano structure, effectively increases and compares table Area.
By the above-mentioned micro-nano Nb of the present invention2O5Powder application is in lithium ion battery electrode material, by Nb2O5Powder and stone Black alkene mixing is as mixing lithium ion battery electrode material, in the electro-chemical test that current density is 0.5C, specific capacitance of discharging Value reaches 158mAh g-1
The useful achievement of the present invention is:
1)The present invention is directed to be designed by rational material microstructure, using this preparation easy to operate, inexpensive of hydro-thermal method Method is realized to Nb2O5The preparation of micro-nanometer structural material powder, by prepared Nb2O5It is uniformly mixed in mortar with graphene Merging is applied does electrode material in lithium-ion battery system, and obtained micro nano structure reduces the ruler of electrode material It is very little, increase its specific surface area and with electrolyte contacts area, mixed with graphene uniform, the excellent electric conductivity of graphene The electric conductivity for improving entire electrode material system is conducive to the transmission of lithium ion in the battery, improves putting for lithium ion battery Electric specific capacity.
2)Nb prepared by the present invention2O5Micro-nano powder material is shown in the electrode test applied to lithium ion battery Very excellent electric discharge specific capacitance, shows 158mAh g under the current density of 0.5C-1Height ratio capacity, in the high current of 5C Under density after 100 cycle charge-discharges, remain to keep 90% or more specific capacitance value.Nb prepared by the present invention2O5It is micro-nano Material has excellent electrochemistry high rate performance and stable circulation performance, can expand electrochemical lithium ion battery electrode material significantly Preparation method and application field.
Description of the drawings
Micro-nano Nb made from Fig. 1 embodiments 12O5The low power scanning electron microscope of powder(SEM)Figure.
Micro-nano Nb made from Fig. 2 embodiments 12O5The high power scanning electron microscope of powder(SEM)Figure.
Micro-nano Nb made from Fig. 3 embodiments 12O5Constant current charge-discharge curve of the powder as lithium ion battery electrode material.
Micro-nano Nb made from Fig. 4 embodiments 12O5Cycle charge-discharge curve of the powder as lithium ion battery electrode material.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
It is dry after using deionized water and ethyl alcohol to clean hydro-thermal reaction axe liner successively;Weigh 1.5mmol NbCl5It is put into hydro-thermal In reaction kettle liner, absolute ethyl alcohol and stirring 30min is added, adds distilled water stirring 30min;Liner is fitted into reaction ax, And it puts into drying box, 230 DEG C of setting drying box temperature, soaking time 20 hours;With deionized water and anhydrous after the completion of reaction Ethyl alcohol eccentric cleaning to neutrality, reactant is removed, is then placed in drying box several times, and setting drying temperature is 60 DEG C, It is 12 hours dry;Dried powder is put into tube furnace, 4 DEG C/min of heating rate is increased to 800 DEG C and calcines 2 hours to obtain the final product.
Embodiment 2
It is dry after using deionized water and ethyl alcohol to clean hydro-thermal reaction axe liner successively;Weigh 1mmol NbCl5It is anti-to be put into hydro-thermal It answers in kettle liner, absolute ethyl alcohol and stirring 30min is added, add distilled water stirring 30min;Liner is fitted into reaction ax, and It puts into drying box, 210 DEG C of setting drying box temperature, soaking time 24 hours;Deionized water and anhydrous second are used after the completion of reaction To neutrality, reactant is removed several times for alcohol eccentric cleaning;It is then placed in drying box, setting drying temperature is 60 DEG C, is done Dry 12 hours;Dried powder is put into tube furnace, 4 DEG C/min of heating rate is increased to 800 DEG C and calcines 2 hours to obtain the final product.
The chemical raw material NbCl used in above example5It is pure to analyze.
Performance test:
1)SEM is tested:The various embodiments described above are prepared into final Nb obtained2O5Micro-nano powder material is in low power and high power SEM It is observed under scanning electron microscope.It is respectively Nb made from embodiment 1 as shown in Figure 1, Figure 22O5The low power and high power of micro-nano powder material Scanning electron microscope (SEM) photograph, it can be seen that Nb in Fig. 12O5It is in granular form and is uniformly distributed, it can be seen that obtained Nb in Fig. 22O5Particle For micron particles, about 1 μm of microns Particle size, and particle surface have apparent micro nano structure, effectively increase specific surface Product;There are gap between particle, be conducive to the entrance of electrolyte to increase the contact area of electrode material and electrolyte.
2)Constant current charge-discharge test:By the last Nb obtained of the various embodiments described above2O5Micro-nano powder material and graphene are equal The even electrode slice that is mixed is assembled into lithium ion battery progress constant current charge-discharge test, wherein Nb2O5It is mixed with both graphenes, Graphene accounts for weight percent 4%.If Fig. 3 is Nb made from embodiment 12O5The electrode that micro-nano powder is mixed with graphene Piece 0.5,1,2,5,10, the cycle charge-discharge curve under the different multiplying of 0.5C, it can be seen that the Nb2O5Micro Nano material exists There is good charge-discharge performance under different multiplying, in the electro-chemical test that current density is 0.5C, electric discharge specific capacitance value reaches To 158mAh g-1
3)Cyclic charging and discharging test:By the last Nb obtained of the various embodiments described above2O5Micro-nano powder material and graphene are equal Even mixing(Graphene accounts for weight percent 4%)Electrode slice is made and is assembled into lithium ion battery progress cyclic charging and discharging test.It is such as attached Fig. 4 is Nb made from embodiment 12O5The cycle charge-discharge curve graph of micro-nano powder material electrodes, under the high current density of 5C After 100 cycle charge-discharges, remain to keep 90% or more specific capacitance value.

Claims (7)

1. a kind of micro-nano Nb for lithium ion battery electrode material2O5Raw powder's production technology, it is characterised in that:The system Preparation Method is hydrothermal method, including step:
1)Weigh NbCl5It is put into hydrothermal reaction kettle liner, absolute ethyl alcohol and stirring certain time is added, add distilled water stirring Same time forms the mixed solution of ethyl alcohol and water;
2)Liner is fitted into reaction ax, is put into drying box, reaction temperature and time are set, carries out hydro-thermal reaction;
3)After the completion of reaction, several times by reactant deionized water and absolute ethyl alcohol eccentric cleaning, it is then placed in drying box, It dries in air;
4)Powder after drying is put into tube furnace, tube furnace is warming up to set temperature, is calcined in air to get with micro- The Nb of nanostructure2O5Powder.
2. the micro-nano Nb according to claim 1 for lithium ion battery electrode material2O5Raw powder's production technology, It is characterized in that:The step 1)Mixing time is 30min, and raw material is made fully to dissolve.
3. the micro-nano Nb according to claim 1 for lithium ion battery electrode material2O5Raw powder's production technology, It is characterized in that:The step 2)Middle reaction temperature is 210 DEG C~230 DEG C, and the reaction time is 20~24 hours.
4. the micro-nano Nb according to claim 1 for lithium ion battery electrode material2O5Raw powder's production technology, It is characterized in that:The step 3)Middle drying temperature is 60 DEG C, and drying time is 12 hours.
5. the micro-nano Nb according to claim 1 for lithium ion battery electrode material2O5Raw powder's production technology, It is characterized in that:The step 4)Middle 4 DEG C/min of tube furnace heating rate, 800 DEG C of set temperature are calcined 2 hours.
6. the micro-nano Nb prepared according to any one of Claims 1 to 5 preparation method2O5Powder, it is characterised in that:It is described Micro-nano Nb2O5Powder is micron particles, and about 1 μm of microns Particle size, particle surface is with apparent micro nano structure.
7. micro-nano Nb according to claim 62O5The application of powder, it is characterised in that:The Nb2O5Powder and graphene Lithium ion battery electrode material is made by mixing into, wherein graphene weight percent is 4%, in the electrification that current density is 0.5C It learns in test, electric discharge specific capacitance value reaches 158mAh g-1
CN201810358785.8A 2018-04-20 2018-04-20 Micro-nano Nb for lithium ion battery electrode material2O5Raw powder's production technology Withdrawn CN108493427A (en)

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Publication number Priority date Publication date Assignee Title
CN109830660A (en) * 2019-01-15 2019-05-31 广州特种承压设备检测研究院 Graphene/niobium pentaoxide combination electrode material and preparation method thereof
CN109950525A (en) * 2019-04-10 2019-06-28 陕西科技大学 A kind of Nb of mao of tripe shape2O5The preparation method of lithium ion battery electrode material
CN109980210A (en) * 2019-04-19 2019-07-05 陕西科技大学 A kind of niobium pentaoxide three-dimensional doped graphene composite material and preparation method and application

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109830660A (en) * 2019-01-15 2019-05-31 广州特种承压设备检测研究院 Graphene/niobium pentaoxide combination electrode material and preparation method thereof
CN109950525A (en) * 2019-04-10 2019-06-28 陕西科技大学 A kind of Nb of mao of tripe shape2O5The preparation method of lithium ion battery electrode material
CN109980210A (en) * 2019-04-19 2019-07-05 陕西科技大学 A kind of niobium pentaoxide three-dimensional doped graphene composite material and preparation method and application
CN109980210B (en) * 2019-04-19 2021-01-29 陕西科技大学 Niobium pentoxide three-dimensional doped graphene composite material and preparation method and application thereof

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Application publication date: 20180904