CN106532001B - A kind of preparation method of the carbon base body support ferriferrous oxide composite material anode material of lithium-ion battery of N doping - Google Patents
A kind of preparation method of the carbon base body support ferriferrous oxide composite material anode material of lithium-ion battery of N doping Download PDFInfo
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- CN106532001B CN106532001B CN201611091260.XA CN201611091260A CN106532001B CN 106532001 B CN106532001 B CN 106532001B CN 201611091260 A CN201611091260 A CN 201611091260A CN 106532001 B CN106532001 B CN 106532001B
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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
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
Urea and soluble trivalent complexing molysite are dissolved in deionized water, are uniformly mixed, solution A is made by a kind of preparation method of the carbon base body support ferriferrous oxide composite material anode material of lithium-ion battery of N doping, in mass ratio 4:1~4:4；Freezing obtains solid B after the pH value of solution A is adjusted to 3~7；2h is pyrolyzed at will being 400~700 DEG C in temperature after solid B freeze-drying.Raw material of the present invention has many advantages, such as environmental-friendly, from a wealth of sources, low in cost, and used preparation method is easily operated.Use trivalent iron salt as the nitrogen source of source of iron and N doping, N doping makes Fe3O4Active site on electrode material increases, and is conducive to the insertion and abjection of sodium ion.The present invention is not added with any surfactant, reacts primary and completes, does not need post-processing.The carbon base body of N doping made from the method supports Fe3O4Composite material, electric conductivity improve, stable cycle performance.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of carbon base body support ferroso-ferric oxide of N doping is compound
The preparation method of material anode material of lithium-ion battery.
Background technique
It is compared in chemical energy storage with lithium ion battery, the cost of raw material of sodium-ion battery is lower than lithium ion battery, and half
Cell potential is higher than lithium ion battery, be suitble to use the lower electrolyte of decomposition voltage, thus security performance be substantially better than lithium from
Sub- battery.Some researches show that transition metal oxide Fe3O4As negative electrode material, theoretical capacity is up to 926mAhg-1, and
Fe3O4Widely distributed, low in cost, asepsis environment-protecting.Therefore, Fe3O4It is a kind of very promising sodium-ion battery cathode
Material.But, Fe identical with most of transition metal oxide negative electrode material3O4There is also some problems, such as volume expansion
Greatly, cyclical stability difference etc..To improve its chemical property, its active sites can be increased by being doped to electrode material
Point improves its electric conductivity with the Material claddings of other good conductivities.
Summary of the invention
The present invention is directed to the problems of the prior art, it is therefore an objective to propose a kind of carbon base body support ferroso-ferric oxide of N doping
The preparation method of composite material anode material of lithium-ion battery, can effectively solve Fe3O4Because of body in poorly conductive, charge and discharge process
The problems such as cycle performance is unstable caused by product expansion is larger, while also solving the problems, such as that high current capacity is low, the preparation
Method is simple to operation, is not added with any organic matter, low in cost, environmental-friendly, is expected to realize industrialized production.
To achieve the above object, technical solution of the present invention is as follows:
A kind of preparation method of the carbon base body support ferriferrous oxide composite material anode material of lithium-ion battery of N doping,
Include the following steps
1) urea and soluble trivalent complexing molysite are dissolved in deionized water by 4:1~4:4 in mass ratio, and mixing is equal
It is even, the suspension A that soluble trivalent complexing iron salt concentration is the mg/mL of 0.5 mg/mL~2 is made；
2) freezing obtains solid B after the pH value of suspension A being adjusted to 3~7；
3) solid B is freeze-dried, obtains product C；
4) product C is pyrolyzed at 400~700 DEG C 2h, obtains the carbon base body support Fe of N doping3O4Composite material sodium from
Sub- cell negative electrode material.
A further improvement of the present invention lies in that soluble trivalent complexing molysite is ferric citrate, ferric acetate in step 1)
Or ammonium ferric oxalate.
A further improvement of the present invention lies in that being uniformly mixed in step 1) is by 10 min of ultrasound under the power of 300W
What~90 min were realized.
A further improvement of the present invention lies in that freezing temperature specifically in refrigerator is to freeze 12 at -20 DEG C in step 2
~for 24 hours.
A further improvement of the present invention lies in that freeze-drying is carried out in freeze drier in step 3), freezing is dry
Dry temperature is -50 DEG C, and the time is 12~24 h.
A further improvement of the present invention lies in that pouring into product C in silica crucible in step 4), quartzy earthenware is wrapped up with tinfoil
Then crucible is pyrolyzed in vacuum tube furnace.
A further improvement of the present invention lies in that with 5~15 DEG C of min in step 4)-1Heating rate from room temperature extremely
400~700 DEG C.
Compared with prior art, the invention has the benefit that raw material of the present invention is with environmental-friendly, next
The advantages that source is extensive, low in cost, used preparation method are easily operated.Use trivalent iron salt as source of iron, N doping makes
Fe3O4Active site on electrode material increases, and is conducive to the insertion and abjection of sodium ion.The present invention uses simple solid phase method
Preparation process is not added with any surfactant, reacts primary and completes, does not need post-processing.N doping made from the method
Carbon base body support Fe3O4Composite material, electric conductivity improve, stable cycle performance, in 0.5A g-1Current density under, charge and discharge
After electricity 100 times, 420mAh g still remain-1Capacity；The carbon base body of N doping prepared by the present invention supports Fe3O4It is multiple
Condensation material, Fe3O4Worm shape particle is evenly distributed in carbon-coating surface, and size is uniform, Fe3O4Have in low angle (111) crystal face and takes
To growth, this interplanar distance is larger, is conducive to sodium ion insertion and abjection when battery charging and discharging, electrode material can be effectively relieved and exist
The volume expansion generated when charge and discharge maintains original pattern, improves the stability of product.N doping increases on carbon base body
Active site, can be in conjunction with more sodium ions, so that battery capacity is improved.Electrode material can be improved in the presence of carbon base body
The electric conductivity of material can shift electronics in time, can also improve the capacity of battery.
Further, present invention employs vacuum tube furnaces is pyrolyzed raw material, can under multiple atmosphere and vacuum work
Make, it is therefore intended that efficiently control the heating rate of reaction.
Detailed description of the invention
Fig. 1 is that the SEM of the embodiment of the present invention 1 schemes, wherein figure (a) is low power figure, and figure (b) is high power figure.
Fig. 2 is the XRD diagram of the embodiment of the present invention 1.
Fig. 3 is the chemical property figure of the embodiment of the present invention 2.
Fig. 4 is that the XPS of the embodiment of the present invention 2 schemes, wherein figure (a) is full spectrogram, and figure (b) is the 2p trajectory diagram of Fe.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
Embodiment 1
1) ratio with mass ratio for 4:1 weighs urea and ferric citrate, and urea and ferric citrate are dissolved in
In deionized water, the suspension A that ironic citrate ammonium concentration is 0.8 mg/mL is made in 30 min of ultrasound under the power of 300W；
2) pH value of suspension A is adjusted to 3, is fallen in surface plate later, is put into refrigerator and is freezed at -20 DEG C
12 h obtain solid solid B；
3) the solid B freezed is put into freeze drier, dry 12 h, the production being completely dried at -50 DEG C
Object C；
4) product C is poured into silica crucible, wraps up silica crucible with tinfoil, puts it into oxide glass tube later
In, electron tubes type furnace temperature and soaking time are set, with 5 DEG C of min-1Heating rate be warming up to 500 DEG C, carry out pyrolysis 2h,
Obtain the carbon base body support Fe of final product N doping3O4Composite material anode material of lithium-ion battery.
The JSM-6700F type scanning electron microscope that resulting product is produced with Japanese firm is observed, from Fig. 1
(a) and in the SEM figure of Fig. 1 (b) it can be seen that the carbon base body of made N doping supports Fe3O4Composite material is to be about by length
The worm shape iron oxide of 300-400 nm is grown on carbon base body, sees Fig. 1.By resulting product particles Rigaku D/
Max2000PCX- x ray diffractometer x analyzes sample, and discovery product is two-phase Fe3O4, see Fig. 2.
Embodiment 2
1) ratio with mass ratio for 4:3 weighs urea and ferric acetate, and urea and ferric acetate are dissolved in deionized water
In, the suspension A that acetic acid concentration of iron is 0.8 mg/mL is made in 30 min of ultrasound under the power of 300W；
2) pH value of suspension A is adjusted to 3, is fallen in surface plate later, is put into refrigerator and is freezed at -20 DEG C
12 h obtain solid solid B；
3) the solid B freezed is put into freeze drier, dry 12 h, the production being completely dried at -50 DEG C
Object C；
4) product C is poured into silica crucible, wraps up silica crucible with tinfoil, puts it into oxide glass tube later
In, electron tubes type furnace temperature and soaking time are set, with 5 DEG C of min-1Heating rate be warming up to 500 DEG C, carry out pyrolysis 2h
Obtain the carbon base body support Fe of final product N doping3O4Composite material anode material of lithium-ion battery.
Resulting product is prepared into button-shaped sodium-ion battery, specific encapsulation step is as follows: by activity powder, conductive agent
Slurry is made after bonding agent (carboxyl methyl cellulose) is according to the proportion grinding uniformly that mass ratio is 8:1:1 in (Super P),
Equably slurry is applied on copper foil with coating device, then in 80 DEG C of vacuum oven dry 12h.Electrode slice is assembled into later
Sodium ion half-cell carries out constant current charge-discharge test to battery using new prestige electrochemical workstation, and test voltage is 0.01 V-
3.0 V, test current density size are 0.1 and 0.5 A g-1, test result is shown in Fig. 3, after the circulation of 100 circles, battery according to
410mAhg can so be kept-1Capacity, it is seen that product under high current, product can still keep high capacity and stability.
By the XPS figure of Fig. 4 (a) and Fig. 4 (b) it can be seen that tetra- kinds of elements containing Fe, O, N and C in the composite material, wherein Fe and O out
It now demonstrates and generates iron oxide in composite material, see Fig. 4.
Embodiment 3
1) urea and soluble trivalent complexing molysite are dissolved in deionized water by 4:1~4:4 in mass ratio, 300W's
The suspension A that soluble trivalent complexing iron salt concentration is 2 mg/mL is made in 10 min of ultrasound under power；Wherein, soluble trivalent
Complexing molysite is ammonium ferric oxalate.
2) temperature is to freeze for 24 hours at -20 DEG C in refrigerator after the pH value of suspension A being adjusted to 5, obtains solid B；
3) solid B is freeze-dried at -50 DEG C in freeze drier 24 h, obtains product C；
4) product C is poured into silica crucible, silica crucible is wrapped up with tinfoil, then with 10 DEG C in vacuum tube furnace
min-1Heating rate from room temperature to 2h is pyrolyzed at 400 DEG C, obtain the carbon base body support Fe of N doping3O4Composite material sodium
Ion battery cathode material.
Embodiment 4
1) urea and soluble trivalent complexing molysite are dissolved in deionized water by 4:2 in mass ratio, in the power of 300W
The suspension A that soluble trivalent complexing iron salt concentration is 0.5 mg/mL is made in lower ultrasonic 90 min；Wherein, soluble trivalent network
Conjunction molysite is ferric acetate.
2) temperature is to freeze 20h at -20 DEG C in refrigerator after the pH value of suspension A being adjusted to 7, obtains solid B；
3) by solid B in freeze drier in -50 DEG C of freeze-drying 20h, obtain product C；
4) product C is poured into silica crucible, silica crucible is wrapped up with tinfoil, then with 15 DEG C in vacuum tube furnace
min-1Heating rate from room temperature to 2h is pyrolyzed at 700 DEG C, obtain the carbon base body support Fe of N doping3O4Composite material sodium
Ion battery cathode material.
Claims (7)
1. a kind of preparation method of the carbon base body support ferriferrous oxide composite material anode material of lithium-ion battery of N doping,
It is characterized in that, includes the following steps
1) urea and soluble trivalent complexing molysite are dissolved in deionized water by 4:1~4:4 in mass ratio, are uniformly mixed, system
The suspension A for being 0.5mg/mL~2mg/mL at soluble trivalent complexing iron salt concentration；
2) freezing obtains solid B after the pH value of suspension A being adjusted to 3~7；
3) solid B is freeze-dried, obtains product C；
4) product C is pyrolyzed at 400~700 DEG C 2h, obtains the carbon base body support Fe of N doping3O4Composite material sodium ion electricity
Pond negative electrode material.
2. a kind of carbon base body support ferriferrous oxide composite material sodium-ion battery of N doping according to claim 1 is negative
The preparation method of pole material, which is characterized in that soluble trivalent complexing molysite is ferric citrate, ferric acetate or grass in step 1)
Sour high-speed rail ammonium.
3. a kind of carbon base body support ferriferrous oxide composite material sodium-ion battery of N doping according to claim 1 is negative
The preparation method of pole material, which is characterized in that in step 1) be uniformly mixed be by under the power of 300W ultrasound 10min~
What 90min was realized.
4. a kind of carbon base body support ferriferrous oxide composite material sodium-ion battery of N doping according to claim 1 is negative
The preparation method of pole material, which is characterized in that in step 2) freezing be specifically in refrigerator temperature be freezing 12 at -20 DEG C~
24h。
5. a kind of carbon base body support ferriferrous oxide composite material sodium-ion battery of N doping according to claim 1 is negative
The preparation method of pole material, which is characterized in that freeze-drying is carried out in freeze drier in step 3), freeze-drying
Temperature be -50 DEG C, the time be 12~for 24 hours.
6. a kind of carbon base body support ferriferrous oxide composite material sodium-ion battery of N doping according to claim 1 is negative
The preparation method of pole material, which is characterized in that product C is poured into silica crucible in step 4), wraps up silica crucible with tinfoil,
Then it is pyrolyzed in vacuum tube furnace.
7. a kind of carbon base body support ferriferrous oxide composite material sodium-ion battery of N doping according to claim 1 is negative
The preparation method of pole material, which is characterized in that with 5~15 DEG C of min in step 4)-1Heating rate from room temperature to 400~
700℃。
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| CN108054367B (en) * | 2017-12-12 | 2020-06-09 | 江西理工大学 | Preparation method of carbon-coated MgFe2O4 negative electrode material for sodium-ion battery |
| CN108306001B (en) * | 2018-01-08 | 2021-04-16 | 北京科技大学 | Lithium ion battery cathode material Fe3O4Preparation method of/N-C |
| CN108400296B (en) * | 2018-02-05 | 2021-05-25 | 北京理工大学 | Heterogeneous element doped ferroferric oxide/graphene negative electrode material |
| CN110224147B (en) * | 2019-07-03 | 2021-11-26 | 河北工业大学 | B. N-codoped C nano-layer and Co nano-particle composite material, and preparation method and application thereof |
| CN113912023B (en) * | 2021-10-08 | 2023-05-23 | 常熟理工学院 | Preparation method of negative electrode material of sodium ion battery |
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| CN105762362B (en) * | 2016-05-23 | 2018-12-11 | 四川大学 | Carbon coated ferriferrous oxide/nitrogen-doped graphene composite material and its application and preparation |
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