CN109616662A - Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery - Google Patents
Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN109616662A CN109616662A CN201811289562.7A CN201811289562A CN109616662A CN 109616662 A CN109616662 A CN 109616662A CN 201811289562 A CN201811289562 A CN 201811289562A CN 109616662 A CN109616662 A CN 109616662A
- Authority
- CN
- China
- Prior art keywords
- nickel
- tungstic acid
- negative electrode
- electrode material
- carries
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Present invention discloses a kind of nickel to carry tungstic acid negative electrode material and preparation method thereof and lithium ion battery, wherein, the preparation method of nickel load tungstic acid negative electrode material, comprising the following steps: the foam nickel material of specified quality is added in the ammonium metatungstate solution of prescribed concentration, obtains reactant；Reactant is subjected to hydrothermal synthesis reaction, nickel is obtained and carries tungstic acid presoma；Nickel load tungstic acid presoma is heat-treated under an inert atmosphere, nickel is obtained and carries tungstic acid negative electrode material.The preparation method that the nickel carries tungstic acid negative electrode material is at low cost, can prepare the tungstic acid negative electrode material with good consistency, electric conductivity and cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, especially relate to a kind of nickel carry tungstic acid negative electrode material and
Preparation method and lithium ion battery.
Background technique
Lithium ion battery is that a kind of new high-tech product because having the characteristics that high-capacity and long-life is widely used in electricity
The fields such as electrical automobile and energy-storage system.
Ev industry is the industry paid close attention to by national policy, and power battery is the core apparatus of energy storage, is had
Environmentally protective advantage, while the disadvantage short there is also course continuation mileage, for the course continuation mileage for improving electric vehicle, major lithium ion is dynamic
Power Battery Company all in the lithium battery of Devoting Major Efforts To Developing high-energy density, lead to common method and be improved positive and negative anodes by raising energy density
Gram volume, raising cell voltage, raising coating weight etc., commercial graphite cathode material used at present, since its is lower
Theoretical specific capacity (372mAh/g) and weaker high rate performance force people to pursue new high performance lithium ionic cell cathode material
Material.
Tungstic acid (WO3), due to theoretical reversible specific capacity (693mAh/g) with higher and rich content, nothing
Poison, to be expected to that graphite is replaced to become negative electrode material of new generation, still, the electric conductivity of tungstic acid is poor, and in charge and discharge
There is a problem of that volume changes greatly and capacity retention ratio difference, causes electrode material to be easy to appear dusting even de- in the process
It falls, so as to shorten the cycle life of tungstic acid.
For problem above existing for tungstic acid negative electrode material, the prior art has revealed that a variety of tungstic acid cathode materials
Material and preparation method thereof, as Chinese invention patent application CN101834290A discloses a kind of tungsten oxide for lithium ion battery
Negative electrode material and preparation method thereof, the material are form of film, are prepared by magnetron sputtering deposition method, made of the film
Electrode has good charging and discharging circulation reversibility, tungsten oxide (WO3) electrode material chemical stability is good, specific capacity is high, charge and discharge
The polarization of level platform is small, preparation method is simple, is suitable for lithium ion battery, but the preparation method institute of this tungsten trioxide cathode material
The instrument and equipment needed is more high-end, and test condition is more demanding and higher cost, is unfavorable for being mass produced；For another example middle promulgated by the State Council
Bright patent application CN107180951A discloses a kind of tungstic acid/tungsten dioxide composite material that can make negative electrode of lithium ion battery
And preparation method thereof, after first citric acid and tungsten source are mixed in proportion, using homogeneous hydro-thermal reaction after be cooled to room temperature,
It obtains can be used as tungstic acid/tungsten dioxide composite material of negative electrode of lithium ion battery, utilizes the metallic conduction of tungsten dioxide
Property, solve the problems, such as that tungstic acid changes greatly in cyclic process there are volume, while improving specific capacity, but this system
Preparation Method product obtained is mixture, is difficult identification specifically any material and plays a role, while WO in product2
With WO3Ratio be difficult to control, therefore the consistency of material is poor.
Therefore, how to obtain that a kind of preparation cost is low, consistency is good, be provided simultaneously with good electric conductivity and cycle performance
Tungstic acid negative electrode material, the technical issues of being those skilled in the art's urgent need to resolve.
Summary of the invention
The main object of the present invention is to provide a kind of nickel to carry tungstic acid negative electrode material and preparation method thereof and lithium-ion electric
Pond, the nickel carry tungstic acid negative electrode material preparation method it is at low cost, can prepare with good consistency, electric conductivity and
The tungstic acid negative electrode material of cycle performance.
The present invention proposes that a kind of nickel carries the preparation method of tungstic acid negative electrode material, comprising the following steps:
The foam nickel material of specified quality is added in the ammonium metatungstate solution of prescribed concentration, reactant is obtained；
Reactant is subjected to hydrothermal synthesis reaction, nickel is obtained and carries tungstic acid presoma；
Nickel load tungstic acid presoma is heat-treated under an inert atmosphere, nickel is obtained and carries tungstic acid negative electrode material.
Further, the foam nickel material of specified quality is added in the ammonium metatungstate solution of prescribed concentration, is obtained anti-
Before the step of answering object, further include the steps that the ammonium metatungstate solution for preparing prescribed concentration, which includes:
Ammonium metawolframate powder is add to deionized water, and is stirred evenly, obtains ammonium metatungstate solution, wherein inclined tungsten
Sour ammonium powder and the mass ratio of deionized water are (0.004~0.006): 1.
Further, reactant is subjected to hydrothermal synthesis reaction, obtains the step of nickel carries tungstic acid presoma, comprising:
Reactant is heated into 20~28h under conditions of temperature is 120 DEG C~180 DEG C, pressure is 1MPa~3MPa, is obtained
Nickel carries tungstic acid presoma.
Further, nickel load tungstic acid presoma is heat-treated under an inert atmosphere, obtains nickel and carries tungstic acid
Before the step of negative electrode material, further include the steps that carrying tungstic acid presoma to nickel is dried, which includes:
Nickel is carried tungstic acid presoma to be 120 DEG C~180 DEG C, dry 2~4h under vacuum condition in temperature.
Further, nickel load tungstic acid presoma is heat-treated under an inert atmosphere, obtains nickel and carries tungstic acid
The step of negative electrode material, comprising:
Nickel is carried into tungstic acid presoma under an inert atmosphere, is warming up to 180 DEG C~200 with the rate of 4 DEG C~6 DEG C/min
It DEG C is calcined, and 2~4h of constant temperature, after being cooled to room temperature, obtains nickel and carry tungstic acid negative electrode material.
Further, the mass ratio of foam nickel material and ammonium metatungstate solution is (0.008~0.012): 1.
Further, inert atmosphere includes any one in nitrogen atmosphere and argon atmosphere.
Further, it is carried in tungstic acid negative electrode material in nickel, the quality accounting of tungstic acid is 5%~20%.
The present invention also proposes that a kind of nickel carries tungstic acid negative electrode material, carries tungstic acid negative electrode material using nickel above-mentioned
Preparation method and obtain.
The present invention also proposes that a kind of lithium ion battery, including anode and cathode, cathode carry tungstic acid using nickel above-mentioned
Negative electrode material preparation.
The beneficial effects of the present invention are:
1, the present invention is prepared nickel using hydrothermal synthesis method and carries tungstic acid negative electrode material, easy to operate, economic and environment-friendly, is fitted
It closes and produces in enormous quantities；
2, selected nickel foam has the characteristics that raw material obtains that simple, resourceful, electric conductivity is excellent, meanwhile, nickel foam
Conductive substrates and reducing agent are potentially acted as, so that the presoma of tungstic acid can be grown directly upon the surface of nickel foam, are alleviated
Mechanical strain/stress bring influences, and alleviates WO3Volume expansion and reuniting effect, to improve leading for negative electrode material
Electrical property and cycle performance.
3, by being heat-treated under an inert atmosphere to the presoma of tungstic acid, so that tungstic acid generated has
There is regular appearance structure, so that negative electrode material has good consistency.
Detailed description of the invention
Fig. 1 is the flow diagram for the preparation method that nickel carries tungstic acid negative electrode material in one embodiment of the invention；
Fig. 2 is the flow diagram for the preparation method that nickel carries tungstic acid negative electrode material in another embodiment of the present invention.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Referring to Fig.1, the embodiment of the present invention proposes that a kind of nickel carries the preparation method of tungstic acid negative electrode material, including following step
It is rapid:
Step 11, the foam nickel material of specified quality is added in the ammonium metatungstate solution of prescribed concentration, is reacted
Object；
Step 12, reactant is subjected to hydrothermal synthesis reaction, obtains nickel and carries tungstic acid presoma；
Step 13, nickel load tungstic acid presoma is heat-treated under an inert atmosphere, it is negative obtains nickel load tungstic acid
Pole material.
In above-mentioned steps 11, the foam nickel material of specified quality is added in the ammonium metatungstate solution of prescribed concentration,
It is used to prepare reactant needed for nickel carries tungstic acid negative electrode material to obtain, so as to later use nickel foam and metatungstic acid ammonia
It carries out redox to answer, generates required nickel and carry tungstic acid negative electrode material, wherein used ammonium metatungstate solution can be
Existing to have certain density ammonium metatungstate solution, be also possible to be prepared in situ has certain density ammonium metatungstate molten
Liquid, it is preferable that the mass ratio of foam nickel material and ammonium metatungstate solution is (0.008~0.012): 1.
In above-mentioned steps 12, reactant is synthesized using hydrothermal synthesis method, it specifically, can be by reactant in temperature
For 120 DEG C~180 DEG C, pressure be 1MPa~3MPa under conditions of heat 20~28h, so that obtaining solid nickel carries tungstic acid
Presoma goes out required nickel load tungstic acid negative electrode material so that the later use nickel carries tungstic acid precursor preparation.
In above-mentioned steps 13, by the purpose that is heat-treated under an inert atmosphere of nickel load tungstic acid presoma be every
Exhausted air prevents the gas componant (such as oxygen) in air from impacting to reaction, so that nickel carries tungstic acid presoma
The nickel load tungstic acid negative electrode material for generating high quality can be heated under an inert atmosphere, it is preferable that nickel is carried into tungstic acid forerunner
Body is warming up to 180 DEG C~200 DEG C with the rate of 4 DEG C~6 DEG C/min and is calcined under nitrogen atmosphere or argon atmosphere, and permanent
2~4h of temperature, after being cooled to room temperature, can be obtained required nickel and carries tungstic acid negative electrode material, wherein carry tungstic acid in nickel
In negative electrode material, the quality accounting of tungstic acid is 5%~20%.
The preparation method that the nickel of the embodiment of the present invention carries tungstic acid negative electrode material has the advantage that
1, the present invention is prepared nickel using hydrothermal synthesis method and carries tungstic acid negative electrode material, easy to operate, economic and environment-friendly, is fitted
It closes and produces in enormous quantities；
2, selected nickel foam has the characteristics that raw material obtains that simple, resourceful, electric conductivity is excellent, meanwhile, nickel foam
Conductive substrates and reducing agent are potentially acted as, so that the presoma of tungstic acid can be grown directly upon the surface of nickel foam, are alleviated
Mechanical strain/stress bring influences, and alleviates WO3Volume expansion and reuniting effect, to improve leading for negative electrode material
Electrical property and cycle performance.
3, by being heat-treated under an inert atmosphere to the presoma of tungstic acid, so that tungstic acid generated has
There is regular appearance structure, so that negative electrode material has good consistency.
Referring to Fig.1 with 2, it is preferable that the foam nickel material of specified quality is added to the ammonium metatungstate solution of prescribed concentration
In, before the step of obtaining reactant, further include the steps that the ammonium metatungstate solution for preparing prescribed concentration, which includes:
Ammonium metawolframate powder is add to deionized water, and is stirred evenly, obtains ammonium metatungstate solution, wherein inclined tungsten
Sour ammonium powder and the mass ratio of deionized water are (0.004~0.006): 1.
In this step 10, by the way that the ammonium metatungstate solution of prescribed concentration is prepared in situ, the purpose of now-making-now-using can reach,
Unnecessary solution storage process is avoided, while solution storage overlong time can be reduced or the improper and bring solution of storage is rotten
Or the contaminated risk of solution.
Referring to Figures 1 and 2, nickel load tungstic acid presoma is heat-treated under an inert atmosphere, obtains nickel and carries three oxygen
Before the step of changing tungsten negative electrode material, further include the steps that carrying tungstic acid presoma to nickel is dried, the step 123 packet
It includes:
Nickel is carried tungstic acid presoma to be 120 DEG C~180 DEG C, dry 2~4h under vacuum condition in temperature.
In this step 123, the purpose that tungstic acid presoma is dried is carried to nickel and is, evaporated and remain in nickel load
The liquid component on tungstic acid presoma surface, the nickel for being conducive to be subsequently formed better quality in this way carry tungstic acid cathode material
Material, wherein tungstic acid presoma is carried to nickel under vacuum conditions and is dried, the evaporation of moisture can be accelerated, to be conducive to
Shorten the dry time, improves the efficiency of production.
The embodiment of the present invention also proposes that a kind of nickel carries tungstic acid negative electrode material, carries tungstic acid cathode using nickel above-mentioned
The preparation method of material and obtain, the nickel carry tungstic acid negative electrode material consistency it is good, be provided simultaneously with good electric conductivity and
Cycle performance.
The embodiment of the present invention also proposes that a kind of lithium ion battery, including anode and cathode, cathode carry three using nickel above-mentioned
Tungsten trioxide cathode material preparation.
The nickel that the above embodiment of the present invention is proposed below with reference to specific embodiment carry tungstic acid negative electrode material and
Preparation method and lithium ion battery are described in more detail.
Embodiment 1
It takes 120mg ammonium metawolframate powder to be added in 30mL deionized water, and stirs evenly, obtain ammonium metatungstate solution simultaneously
It transfers them in autoclave；
It takes 33mg foam nickel material to be added in ammonium metatungstate solution, obtains reactant；
Autoclave equipped with reactant is put into the baking oven that temperature is 150 DEG C and is heated for 24 hours, nickel is obtained and carries three oxygen
Change tungsten presoma, wherein the pressure in heating process mesohigh reaction kettle is 1MPa；
The reaction kettle for carrying tungstic acid presoma equipped with nickel is transferred to dry in the vacuum oven that temperature is 150 DEG C
4h；
By after drying nickel carry tungstic acid presoma in a nitrogen atmosphere, with the rate of 5 DEG C/min be warming up to 200 DEG C into
Row calcining, and constant temperature 2h after being cooled to room temperature, obtain nickel and carry tungstic acid negative electrode material, chemical formula WO3/ NF,
In, the quality of tungstic acid is that nickel carries the 5%~20% of tungstic acid negative electrode material quality.
Embodiment 2
It takes 140mg ammonium metawolframate powder to be added in 30mL deionized water, and stirs evenly, obtain ammonium metatungstate solution simultaneously
It transfers them in autoclave；
It takes 33mg foam nickel material to be added in ammonium metatungstate solution, obtains reactant；
Autoclave equipped with reactant is put into the baking oven that temperature is 150 DEG C and is heated for 24 hours, nickel is obtained and carries three oxygen
Change tungsten presoma, wherein the pressure in heating process mesohigh reaction kettle is 1MPa；
The reaction kettle for carrying tungstic acid presoma equipped with nickel is transferred to dry in the vacuum oven that temperature is 150 DEG C
4h；
By after drying nickel carry tungstic acid presoma in a nitrogen atmosphere, with the rate of 5 DEG C/min be warming up to 200 DEG C into
Row calcining, and constant temperature 2h after being cooled to room temperature, obtain nickel and carry tungstic acid negative electrode material, chemical formula WO3/ NF,
In, the quality of tungstic acid is that nickel carries the 5%~20% of tungstic acid negative electrode material quality.
Embodiment 3
It takes 160mg ammonium metawolframate powder to be added in 30mL deionized water, and stirs evenly, obtain ammonium metatungstate solution simultaneously
It transfers them in autoclave；
It takes 33mg foam nickel material to be added in ammonium metatungstate solution, obtains reactant；
Autoclave equipped with reactant is put into the baking oven that temperature is 150 DEG C and is heated for 24 hours, nickel is obtained and carries three oxygen
Change tungsten presoma, wherein the pressure in heating process mesohigh reaction kettle is 1MPa；
The reaction kettle for carrying tungstic acid presoma equipped with nickel is transferred to dry in the vacuum oven that temperature is 150 DEG C
4h；
By after drying nickel carry tungstic acid presoma in a nitrogen atmosphere, with the rate of 5 DEG C/min be warming up to 200 DEG C into
Row calcining, and constant temperature 2h after being cooled to room temperature, obtain nickel and carry tungstic acid negative electrode material, chemical formula WO3/ NF,
In, the quality of tungstic acid is that nickel carries the 5%~20% of tungstic acid negative electrode material quality.
Embodiment 4
It takes 140mg ammonium metawolframate powder to be added in 30mL deionized water, and stirs evenly, obtain ammonium metatungstate solution simultaneously
It transfers them in autoclave；
It takes 33mg foam nickel material to be added in ammonium metatungstate solution, obtains reactant；
Autoclave equipped with reactant is put into the baking oven that temperature is 150 DEG C and is heated for 24 hours, nickel is obtained and carries three oxygen
Change tungsten presoma, wherein the pressure in heating process mesohigh reaction kettle is 1MPa；
The reaction kettle for carrying tungstic acid presoma equipped with nickel is transferred to dry in the vacuum oven that temperature is 120 DEG C
4h；
By after drying nickel carry tungstic acid presoma in a nitrogen atmosphere, with the rate of 5 DEG C/min be warming up to 200 DEG C into
Row calcining, and constant temperature 2h after being cooled to room temperature, obtain nickel and carry tungstic acid negative electrode material, chemical formula WO3/ NF,
In, the quality of tungstic acid is that nickel carries the 5%~20% of tungstic acid negative electrode material quality.
Embodiment 5
It takes 140mg ammonium metawolframate powder to be added in 30mL deionized water, and stirs evenly, obtain ammonium metatungstate solution simultaneously
It transfers them in autoclave；
It takes 33mg foam nickel material to be added in ammonium metatungstate solution, obtains reactant；
Autoclave equipped with reactant is put into the baking oven that temperature is 150 DEG C and is heated for 24 hours, nickel is obtained and carries three oxygen
Change tungsten presoma, wherein the pressure in heating process mesohigh reaction kettle is 1MPa；
The reaction kettle for carrying tungstic acid presoma equipped with nickel is transferred to dry in the vacuum oven that temperature is 180 DEG C
4h；
By after drying nickel carry tungstic acid presoma in a nitrogen atmosphere, with the rate of 5 DEG C/min be warming up to 200 DEG C into
Row calcining, and constant temperature 2h after being cooled to room temperature, obtain nickel and carry tungstic acid negative electrode material, chemical formula WO3/ NF,
In, the quality of tungstic acid is that nickel carries the 5%~20% of tungstic acid negative electrode material quality.
The nickel being prepared according to embodiment 1-5 carries tungstic acid negative electrode material and battery is made in existing method and tests
Its specific capacity, specific battery preparation method are as follows: obtained nickel is carried tungstic acid negative electrode material (the quality accounting of tungstic acid
It is 5%~20%) electrode preparation is carried out, and be assembled into button cell and carry out storage lithium performance study, wherein active material: conductive
Carbon black: the mass ratio of PVDF is 8:1:1, and diaphragm Celgard2300, electrolyte is 1MLiPF6 (volume ratio EC:DEC:EMC
=1:1:1), metal lithium sheet is used as to electrode and reference electrode, and voltage window is 0.01~4.00V, is assembled into 2032 type knobs
Battery is detained, button cell is placed in the LRH-250 model insulating box of Shanghai Hui Tai instrument manufacturing Co., Ltd production, setting temperature
Degree is 25 DEG C of constant temperature, is carried out in the RepowerCDS-GGS test cabinet of Rui Neng Industry Co., Ltd, Shenzhen,
Charge-discharge test is carried out under the conditions of under the electric current of 150mA/g, the electrochemical test data of related embodiment refers to table 1.
Table 1
As shown in Table 1, the lithium ion battery of tungstic acid negative electrode material preparation is carried using the nickel that embodiment 1 is prepared,
Reversible specific capacity is up to 690mAh/g for the first time for it, its reversible specific capacity is positively retained at 650mAh/g after recycling 50 times；Using implementation
The nickel that example 2 is prepared carries the lithium ion battery of tungstic acid negative electrode material preparation, and reversible specific capacity is up to 682mAh/ for the first time
G, its reversible specific capacity is positively retained at 655mAh/g after recycling 50 times；It is negative that tungstic acid is carried using the nickel that embodiment 3 is prepared
The lithium ion battery of pole material preparation, reversible specific capacity is up to 685mAh/g for the first time, its reversible specific capacity can after recycling 50 times
It is maintained at 656mAh/g；The lithium ion battery of tungstic acid negative electrode material preparation is carried using the nickel that embodiment 4 is prepared, it is first
Secondary reversible specific capacity is up to 705mAh/g, its reversible specific capacity is positively retained at 665mAh/g after recycling 50 times；It is made using embodiment 5
Standby obtained nickel carries the lithium ion battery of tungstic acid negative electrode material preparation, and reversible specific capacity is followed up to 690mAh/g for the first time
Its reversible specific capacity is positively retained at 660mAh/g after ring 50 times；Therefore, the nickel of the application carries the preparation of tungstic acid negative electrode material
For method by being supported on tungstic acid in the nickel foam with high conductivity, can get has height ratio capacity and good circulation
The nickel of energy carries tungstic acid negative electrode material, and then improves the chemical property of lithium ion battery.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content is applied directly or indirectly in other correlations
Technical field, be included within the scope of the present invention.
Claims (10)
1. the preparation method that a kind of nickel carries tungstic acid negative electrode material, which comprises the following steps:
The foam nickel material of specified quality is added in the ammonium metatungstate solution of prescribed concentration, reactant is obtained；
The reactant is subjected to hydrothermal synthesis reaction, nickel is obtained and carries tungstic acid presoma；
Nickel load tungstic acid presoma is heat-treated under an inert atmosphere, nickel is obtained and carries tungstic acid negative electrode material.
2. the preparation method that nickel according to claim 1 carries tungstic acid negative electrode material, which is characterized in that described to specify
It further include system before the step of foam nickel material of quality is added in the ammonium metatungstate solution of prescribed concentration, obtains reactant
The step of ammonium metatungstate solution of standby prescribed concentration, which includes:
Ammonium metawolframate powder is add to deionized water, and is stirred evenly, obtains the ammonium metatungstate solution, wherein described
Ammonium metawolframate powder and the mass ratio of the deionized water are (0.004~0.006): 1.
3. the preparation method that nickel according to claim 1 carries tungstic acid negative electrode material, which is characterized in that it is described will be described
Reactant carries out hydrothermal synthesis reaction, obtains the step of nickel carries tungstic acid presoma, comprising:
The reactant is heated into 20~28h under conditions of temperature is 120 DEG C~180 DEG C, pressure is 1MPa~3MPa, is obtained
The nickel carries tungstic acid presoma.
4. the preparation method that nickel according to claim 1 carries tungstic acid negative electrode material, which is characterized in that it is described will be described
Nickel carries tungstic acid presoma and is heat-treated under an inert atmosphere, before obtaining the step of nickel carries tungstic acid negative electrode material,
Further include the steps that carrying tungstic acid presoma to the nickel is dried, which includes:
The nickel is carried tungstic acid presoma to be 120 DEG C~180 DEG C, dry 2~4h under vacuum condition in temperature.
5. the preparation method that nickel according to claim 1 carries tungstic acid negative electrode material, which is characterized in that it is described will be described
Nickel carries tungstic acid presoma and is heat-treated under an inert atmosphere, obtains the step of nickel carries tungstic acid negative electrode material, comprising:
The nickel is carried into tungstic acid presoma under an inert atmosphere, is warming up to 180 DEG C~200 with the rate of 4 DEG C~6 DEG C/min
It DEG C is calcined, and 2~4h of constant temperature, after being cooled to room temperature, obtains the nickel and carry tungstic acid negative electrode material.
6. the preparation method that nickel according to any one of claims 1 to 5 carries tungstic acid negative electrode material, which is characterized in that
The mass ratio of the foam nickel material and the ammonium metatungstate solution is (0.008~0.012): 1.
7. the preparation method that nickel according to any one of claims 1 to 5 carries tungstic acid negative electrode material, which is characterized in that
The inert atmosphere includes any one in nitrogen atmosphere and argon atmosphere.
8. the preparation method that nickel according to any one of claims 1 to 5 carries tungstic acid negative electrode material, which is characterized in that
It is carried in tungstic acid negative electrode material in the nickel, the quality accounting of tungstic acid is 5%~20%.
9. a kind of nickel carries tungstic acid negative electrode material, which is characterized in that carry three using the described in any item nickel of claim 1 to 8
The preparation method of tungsten trioxide cathode material and obtain.
10. a kind of lithium ion battery, which is characterized in that including anode and cathode, the cathode uses nickel as claimed in claim 9
Carry the preparation of tungstic acid negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289562.7A CN109616662A (en) | 2018-10-31 | 2018-10-31 | Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289562.7A CN109616662A (en) | 2018-10-31 | 2018-10-31 | Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109616662A true CN109616662A (en) | 2019-04-12 |
Family
ID=66002909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811289562.7A Pending CN109616662A (en) | 2018-10-31 | 2018-10-31 | Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109616662A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841589A (en) * | 2020-07-29 | 2020-10-30 | 浙江理工大学 | Nickel-cobalt-tungsten phosphide catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789550A (en) * | 2016-04-26 | 2016-07-20 | 熊菊莲 | Electrode and preparation method of electrode material |
| CN105895882A (en) * | 2016-06-02 | 2016-08-24 | 广西大学 | Preparation method for nitrogen-doped graphene-coated nickel sulfide composite electrode material |
| CN106611847A (en) * | 2017-01-13 | 2017-05-03 | 昆明理工大学 | Preparation method of titanium-doped nano tungsten oxide negative electrode material |
| CN108598439A (en) * | 2018-05-14 | 2018-09-28 | 昆明理工大学 | A kind of preparation method of tungstic acid/graphene composite negative pole |
-
2018
- 2018-10-31 CN CN201811289562.7A patent/CN109616662A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789550A (en) * | 2016-04-26 | 2016-07-20 | 熊菊莲 | Electrode and preparation method of electrode material |
| CN105895882A (en) * | 2016-06-02 | 2016-08-24 | 广西大学 | Preparation method for nitrogen-doped graphene-coated nickel sulfide composite electrode material |
| CN106611847A (en) * | 2017-01-13 | 2017-05-03 | 昆明理工大学 | Preparation method of titanium-doped nano tungsten oxide negative electrode material |
| CN108598439A (en) * | 2018-05-14 | 2018-09-28 | 昆明理工大学 | A kind of preparation method of tungstic acid/graphene composite negative pole |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841589A (en) * | 2020-07-29 | 2020-10-30 | 浙江理工大学 | Nickel-cobalt-tungsten phosphide catalyst and preparation method and application thereof |
| CN111841589B (en) * | 2020-07-29 | 2023-07-25 | 浙江理工大学 | Nickel-cobalt-tungsten phosphide catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110112388B (en) | Porous tungsten trioxide coated modified positive electrode material and preparation method thereof | |
| CN107492643A (en) | A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof | |
| CN103682304A (en) | Lithium-rich solid solution anode composite and preparation method thereof, lithium ion battery anode plate and lithium ion battery | |
| CN107681147B (en) | Preparation method and application of solid electrolyte coated modified lithium ion battery positive electrode material | |
| CN109461906B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN106935830B (en) | lithium ion battery composite positive electrode material and preparation method and application thereof | |
| CN109449379A (en) | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof | |
| CN108807941B (en) | Preparation method and application of iron phosphide nanosheet and biomass carbon composite material | |
| CN105226267A (en) | Three dimensional carbon nanotubes modifies spinel nickel lithium manganate material and its preparation method and application | |
| CN105680050B (en) | A kind of cell negative electrode material of 2-methylimidazole zinc salt pyrolysis gained | |
| CN107887583A (en) | A kind of doped lithium iron phosphate anode material and preparation method thereof | |
| CN112909247A (en) | Zinc ion battery positive electrode material, preparation method and application thereof, and zinc ion battery | |
| CN113937262A (en) | Metal oxide modified positive electrode material for sodium ion battery and preparation method and application thereof | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| CN108264099B (en) | A kind of preparation method of lithium ion battery high-performance two-dimensional sheet nickel oxide negative electrode material | |
| CN108847481A (en) | A kind of preparation and application of the porous manganese sesquioxide managnic oxide cube negative electrode material of high performance lithium ion battery carbon coating | |
| CN108767231A (en) | L iNixCoyMnl-x-yO2/Li2O·B2O3Preparation method of composite positive electrode material | |
| CN115939361B (en) | Copper phosphide doped hard carbon composite material and preparation method thereof | |
| CN107195884A (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| CN104600294B (en) | High-capacity microrod lithium manganese iron phosphate material synthesized by hydrothermal process and preparation method thereof | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN109309228B (en) | Positive electrode active material, preparation method, positive electrode and high-specific-energy power battery | |
| CN109616662A (en) | Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery | |
| CN109987607B (en) | Mesoporous silicon/cobalt disilicide composite microsphere material and preparation method and application thereof | |
| CN113422014A (en) | Polyaniline-coated tin dioxide composite negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190412 |