CN108281636A - A kind of preparation method and applications of coated by titanium dioxide ferric oxide composite material - Google Patents
A kind of preparation method and applications of coated by titanium dioxide ferric oxide composite material Download PDFInfo
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- CN108281636A CN108281636A CN201810080490.9A CN201810080490A CN108281636A CN 108281636 A CN108281636 A CN 108281636A CN 201810080490 A CN201810080490 A CN 201810080490A CN 108281636 A CN108281636 A CN 108281636A
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- titanium dioxide
- iron trioxide
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- ferric oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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 present invention relates to a kind of preparation method and applications of coated by titanium dioxide ferric oxide composite material, di-iron trioxide microballoon is synthesized using hydro-thermal method, then one layer of unformed titanium dioxide is coated on di-iron trioxide microballoon by dynamics Controlling immersion method, the crystal type coated by titanium dioxide di-iron trioxide composite lithium ion battery cathode material with nucleocapsid is then thermally treated resulting in air atmosphere.Coated by titanium dioxide di-iron trioxide composite negative pole material prepared by the method effectively combines the height ratio capacity of di-iron trioxide and the excellent cycling stability of titanium dioxide, to the cycle performance for showing higher specific capacity and stablizing, a kind of ideal lithium ion battery negative material, can be widely applied to need high-energy density, service life is long, on lithium-ion-power cell of high stability.The method of the present invention is simple simultaneously, and mild condition, cost is relatively low, and material morphology structure is easy to regulate and control, and easily mass produces, has a good application prospect.
Description
Technical field
The invention belongs to lithium ion battery new energy Material Fields, and in particular to a kind of coated by titanium dioxide di-iron trioxide is multiple
The preparation method and applications of condensation material.
Background technology
Lithium ion battery conduct one kind is novel, green, high-energy chemistry power supply is widely used in portable electronic device,
The fields such as electric vehicle, aerospace.With the development of society, people are to performance of lithium ion battery, more stringent requirements are proposed.
Important composition of the negative material as lithium ion battery, plays an important role to the overall performance of battery.Commercial Li-ion at present
The graphite-based negative material specific capacity that battery uses is usually less than 350 mAh g-1, this lower specific capacity is difficult to meet reality
Growth requirement.In addition, the intercalation potential of this graphite-based negative material is relatively low, and it is close with lithium metal, in continuous charge and discharge
Li dendrite is easy tod produce in electric process, so as to cause battery short circuit, causes safety problem.Therefore, it researches and develops novel, efficient
Negative material it is extremely urgent.
In recent years, transition metal oxide（Such as Fe2O3、Fe3O4、NiO、Co3O4Deng）Because its specific capacity is high, derives from a wealth of sources
The advantages that be considered as a kind of very promising lithium ion battery negative material and be concerned.Wherein Fe2O3Theory
Specific capacity is up to 1008 mAh g-1, it is equivalent to 3 times of conventional graphite base cathode specific capacity.Meanwhile source of iron is with nontoxic, cheap
The advantages that being easy to get.Thus, di-iron trioxide material by as a kind of efficient negative material by numerous studies.However, three oxidations
The electron-transport of two iron materials is slower, causes high rate performance bad.Meanwhile di-iron trioxide material meeting in charge and discharge process
There is larger volume change, lead to caving in for material structure, causes the rapid decay of capacity.
Titanic oxide material is as lithium ion battery negative material, and removal lithium embedded voltage platform is in 1.75V or so, Ke Yiyou
The generation for avoiding Li dendrite of effect, improves the safe to use of battery.In addition, titanyl forms octahedral structure, in charge and discharge
Volume change is smaller in the process, can be very good the integrality of holding structure, to obtain preferable stable cycle performance.
For this purpose, to Fe2O3Effective cladding that material carries out titanium dioxide can fully combine Fe2O3Height ratio capacity and two
The rock-steady structure of titanium oxide is effectively improved the disadvantages mentioned above of di-iron trioxide material, a kind of with high specific capacity to obtain
With the composite material of excellent cycling performance.
Invention content
It is an object of the invention to overcome disadvantage existing in the prior art, provide that a kind of specific capacity is high and cycle performance is steady
The preparation method and applications of fixed coated by titanium dioxide ferric oxide composite material.
In order to solve the above technical problems, the technical scheme is that：A kind of coated by titanium dioxide di-iron trioxide is compound
The preparation method of material, it is characterised in that include the following steps：
Step 1：A certain amount of Fe(NO3)39H2O is weighed, is dissolved in the mixed solution of a certain amount of glycerine and absolute ethyl alcohol,
Stirring and dissolving obtains orange solution；
Step 2：The orange solution that step 1 obtains is transferred in 50ml water heating kettles at 160~200 DEG C and reacts 12~24
Hour, then washed, centrifugation, 60 DEG C of drying obtain the di-iron trioxide material of light red；
Step 3：The di-iron trioxide material obtained in 0.075g step 2 is weighed, is dissolved in 100ml absolute ethyl alcohols, then
Appropriate a concentration of 28% ammonia spirit is added, then the solution of tetrabutyl titanate of certain volume is slowly added dropwise in ultrasound 15 minutes；
Step 4：The mixed solution that step 3 is obtained in 45 DEG C of water-baths 12~36 hours, then washing, centrifuge,
60 DEG C are dried to obtain unformed coated by titanium dioxide di-iron trioxide material；
Step 5：It is small that the di-iron trioxide material that step 4 obtains is warming up to 400~800 DEG C of heat preservations 3~6 in air atmosphere
When, it is cooled to room temperature, obtains final coated by titanium dioxide di-iron trioxide composite negative pole material.
Iron concentration is 0.02~0.10mol/L in the step 1.
The control of the volume ratio of glycerine and absolute ethyl alcohol is 1 in the step 1：1~8.
The volume ratio of butyl titanate and absolute ethyl alcohol is 0.6~1.2 in the step 3：100.
The volume ratio of ammonia spirit and absolute ethyl alcohol is 0.2~0.5 in the step 3：100.
The application of above-mentioned coated by titanium dioxide ferric oxide composite material, which is characterized in that the titanium dioxide obtained
Titanium coats ferric oxide composite material and acetylene black, PVDF, in mass ratio 8:1:1 is mixed, and slurry is made, and is uniformly coated
On copper foil, circular electrode pole piece is stamped into after 24 hours through 120 DEG C of vacuum dryings.
The present invention first uses di-iron trioxide microballoon of the hydro-thermal method synthesis with porous structure, then passes through dynamics Controlling
Immersion method coats one layer of unformed titanic oxide material in di-iron trioxide microsphere surface, by being thermally treated resulting in titanium dioxide
Coat di-iron trioxide composite negative pole material.The advantage of the invention is that preparation condition is simply mild, equipment requirement is low, technique road
Line is simple, and large-scale production, obtained coated by titanium dioxide di-iron trioxide composite negative pole material is convenient for have higher ratio
Capacity and the cycle performance stablized, therefore have a good application prospect.
Description of the drawings
Fig. 1 is the XRD diagram of coated by titanium dioxide di-iron trioxide composite negative pole material prepared by embodiment 1；
Fig. 2 is 50000 times of scanning electron microscope (SEM) photographs of coated by titanium dioxide di-iron trioxide composite negative pole material prepared by embodiment 2
Piece；
Fig. 3 is 10000 times of scanning electron microscope (SEM) photographs of coated by titanium dioxide di-iron trioxide composite negative pole material prepared by embodiment 3
Piece；
Fig. 4 is the transmission electron micrograph of coated by titanium dioxide di-iron trioxide composite negative pole material prepared by embodiment 4；
Fig. 5 is the preceding cyclic voltammetry curve three times of coated by titanium dioxide di-iron trioxide composite negative pole material prepared by embodiment 4.
Specific implementation mode
It is of the invention to reach the technological means and effect that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to the preparation method of a kind of coated by titanium dioxide ferric oxide composite material that proposes according to the present invention and its
Specific implementation mode, method, step, feature and its effect of application, detailed description are as follows：
Implementation column 1：
It weighs 0.32g Fe(NO3)39H2Os and is dissolved in 5ml glycerine with 35ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration is 0.02 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, 24 is reacted at 170 DEG C
Hour, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；It is micro- to weigh 0.075g di-iron trioxides
Ball is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol volume
0.2%, ultrasound 15 minutes is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）The dosage of solution, TBOT is
The 0.6% of absolute ethyl alcohol, control are added dropwise completely, then mixed solution are transferred in 45 DEG C of water-bath devices in 5 minutes,
Reaction 24 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed titanium dioxide
Titanium coats ferric oxide composite material；Finally in air atmosphere, 4 hours are kept the temperature for 400 DEG C, is cooled to room temperature, obtains dioxy
Change titanium and coats di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 942 mAh g after recycling 50 times-1, discharge capacity is 1315 mAh g for the first time-1, charging
Capacity is 863 mAh g-1。
Implementation column 2：
It weighs 0.32g Fe(NO3)39H2Os and is dissolved in 14ml glycerine with 26ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration be 0.02 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, is reacted at 180 DEG C
12 hours, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；Weigh 0.075g di-iron trioxides
Microballoon is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol volume
0.4%, ultrasound 15 minutes, be then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）Solution, the dosage of TBOT
It is the 0.75% of absolute ethyl alcohol, control is added dropwise completely in 5 minutes, and mixed solution is then transferred to 45 DEG C of water-bath devices
In, reaction 15 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed dioxy
Change titanium and coats ferric oxide composite material；Finally in air atmosphere, 5 hours are kept the temperature for 500 DEG C, is cooled to room temperature, obtains two
Titanium-oxide-coated di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 714 mAh g after recycling 50 times-1, discharge capacity is 1025 mAh g for the first time-1, charging
Capacity is 812 mAh g-1。
Implementation column 3：
It weighs 0.64g Fe(NO3)39H2Os and is dissolved in 5ml glycerine with 35ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration is 0.04 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, 24 is reacted at 180 DEG C
Hour, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；It is micro- to weigh 0.075g di-iron trioxides
Ball is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol volume
0.5%, ultrasound 15 minutes is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）The dosage of solution, TBOT is
The 0.75% of absolute ethyl alcohol, control are added dropwise completely, then mixed solution are transferred in 45 DEG C of water-bath devices in 5 minutes,
Reaction 26 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed titanium dioxide
Titanium coats ferric oxide composite material；Finally in air atmosphere, 6 hours are kept the temperature for 600 DEG C, is cooled to room temperature, obtains dioxy
Change titanium and coats di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 738 mAh g after recycling 50 times-1, discharge capacity is 1065 mAh g for the first time-1, charging
Capacity is 822 mAh g-1。
Implementation column 4：
It weighs 0.5g Fe(NO3)39H2Os and is dissolved in 8ml glycerine with 32ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration is 0.03 mol/ orange solutions；Weighing 0.5g Fe(NO3)39H2Os, to be dissolved in 5ml glycerine anhydrous with 35ml
In ethyl alcohol, orange solution is obtained by stirring and dissolving；Then mixed solution is transferred in 50 milliliters of water heating kettles, it is anti-at 190 DEG C
Answer 24 hours, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；Weigh the oxidations of 0.075g tri- two
Iron microballoon is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol body
Long-pending 0.3%, ultrasound 15 minutes, is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）Solution, the use of TBOT
Amount is the 0.75% of absolute ethyl alcohol, and control is added dropwise completely in 5 minutes, and mixed solution is then transferred to 45 DEG C of water-bath dresses
In setting, reaction 30 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed two
Titanium-oxide-coated ferric oxide composite material；Finally in air atmosphere, 4 hours are kept the temperature for 700 DEG C, is cooled to room temperature, obtains
Coated by titanium dioxide di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 752mAh g after recycling 50 times-1, discharge capacity is 1185 mAh g for the first time-1, charging appearance
Amount is 824 mAh g-1。
Implementation column 5：
It weighs 1.12g Fe(NO3)39H2Os and is dissolved in 5ml glycerine with 35ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration is 0.07 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, 24 is reacted at 180 DEG C
Hour, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；It is micro- to weigh 0.075g di-iron trioxides
Ball is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol volume
0.3%, ultrasound 15 minutes is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）The dosage of solution, TBOT is
The 0.75% of absolute ethyl alcohol, control are added dropwise completely, then mixed solution are transferred in 45 DEG C of water-bath devices in 5 minutes,
Reaction 35 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed titanium dioxide
Titanium coats ferric oxide composite material；Finally in air atmosphere, 4 hours are kept the temperature for 800 DEG C, is cooled to room temperature, obtains dioxy
Change titanium and coats di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 920mAh g after recycling 50 times-1, discharge capacity is 1260 mAh g for the first time-1, charging appearance
Amount is 886 mAh g-1。
Implementation column 6：
It weighs 0.32g Fe(NO3)39H2Os and is dissolved in 5ml glycerine with 35ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration is 0.02 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, 15 is reacted at 180 DEG C
Hour, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；It is micro- to weigh 0.075g di-iron trioxides
Ball is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol volume
0.3%, ultrasound 15 minutes is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）The dosage of solution, TBOT is
The 0.9% of absolute ethyl alcohol, control are added dropwise completely, then mixed solution are transferred in 45 DEG C of water-bath devices in 5 minutes,
Reaction 12 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed titanium dioxide
Titanium coats ferric oxide composite material；Finally in air atmosphere, 6 hours are kept the temperature for 800 DEG C, is cooled to room temperature, obtains dioxy
Change titanium and coats di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 762 mAh g after recycling 50 times-1, discharge capacity is 1056 mAh g for the first time-1, charging
Capacity is 812 mAh g-1。
Implementation column 7：
0.32g Fe(NO3)39H2Os are weighed to be dissolved in 4.5ml glycerine and 35.5ml absolute ethyl alcohols, stir evenly to be formed iron from
The molar concentration of son is 0.02 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, it is anti-at 180 DEG C
Answer 20 hours, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；Weigh the oxidations of 0.075g tri- two
Iron microballoon is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol body
Long-pending 0.3%, ultrasound 15 minutes, is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）Solution, the use of TBOT
Amount is the 1.2% of absolute ethyl alcohol, and control is added dropwise completely in 5 minutes, and mixed solution is then transferred to 45 DEG C of water-bath devices
In, reaction 24 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed dioxy
Change titanium and coats ferric oxide composite material；Finally in air atmosphere, 4 hours are kept the temperature for 600 DEG C, is cooled to room temperature, obtains two
Titanium-oxide-coated di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 706mAh g after recycling 50 times-1, discharge capacity is 986 mAh g for the first time-1, charging appearance
Amount is 745 mAh g-1。
Implementation column 8：
It weighs 0.32g Fe(NO3)39H2Os and is dissolved in 20ml glycerine with 20ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration be 0.02 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, is reacted at 180 DEG C
24 hours, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；Weigh 0.075g di-iron trioxides
Microballoon is dissolved in 100ml absolute ethyl alcohols, and a concentration of 28% ammonia spirit is then added, and ammonia volume is absolute ethyl alcohol volume
0.3%, ultrasound 15 minutes, be then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）Solution, the dosage of TBOT
It is the 0.75% of absolute ethyl alcohol, control is added dropwise completely in 5 minutes, and mixed solution is then transferred to 45 DEG C of water-bath devices
In, reaction 24 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed dioxy
Change titanium and coats ferric oxide composite material；Finally in air atmosphere, 4 hours are kept the temperature for 600 DEG C, is cooled to room temperature, obtains two
Titanium-oxide-coated di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 763mAh g after recycling 50 times-1, discharge capacity is 978 mAh g for the first time-1, charging appearance
Amount is 769 mAh g-1。
Implementation column 9：
It weighs 1.6g Fe(NO3)39H2Os and is dissolved in 5ml glycerine with 35ml absolute ethyl alcohols, stir evenly to form iron ion
Molar concentration is 0.1 mol/ orange solutions；Then mixed solution is transferred in 50 milliliters of water heating kettles, it is small that 24 is reacted at 180 DEG C
When, subsequent natural cooling, washing, centrifugation, 60 DEG C be dried to obtain di-iron trioxide microballoon；Weigh 0.075g di-iron trioxide microballoons
It is dissolved in 100ml absolute ethyl alcohols, a concentration of 28% ammonia spirit is then added, ammonia volume is absolute ethyl alcohol volume
0.3%, ultrasound 15 minutes is then slowly added to butyl titanate in the case where stirring stirring condition（TBOT）The dosage of solution, TBOT is
The 0.75% of absolute ethyl alcohol, control are added dropwise completely, then mixed solution are transferred in 45 DEG C of water-bath devices in 5 minutes,
Reaction 24 hours is carried out under stirring conditions.It then centrifuged, washed, being detached, 60 DEG C of drying obtain unformed titanium dioxide
Titanium coats ferric oxide composite material；Finally in air atmosphere, 4 hours are kept the temperature for 600 DEG C, is cooled to room temperature, obtains dioxy
Change titanium and coats di-iron trioxide composite negative pole material powder.
By coated by titanium dioxide ferric oxide composite material, acetylene black and PVDF obtained with mass ratio for 8:1:1 into
Row mixing, is made slurry, is coated uniformly on copper foil, 120 DEG C of vacuum dryings are stamped into circular electrode pole piece after 24 hours, with gold
It is to electrode, 1 mol/L LiPF to belong to lithium piece6/ DMC+EC（Volume ratio is 1: 1）For electrolyte, Celgard 2300 be every
Film is assembled into button cell and carries out electro-chemical test, ranging from 0. 01~3. 0 V of charging/discharging voltage.In 100 mA
g-1Its reversible capacity is still maintained at 815mAh g after recycling 50 times-1, discharge capacity is 1002 mAh g for the first time-1, charging appearance
Amount is 849 mAh g-1。
Claims (6)
1. a kind of preparation method of coated by titanium dioxide ferric oxide composite material, it is characterised in that include the following steps：
Step 1：A certain amount of Fe(NO3)39H2O is weighed, is dissolved in the mixed solution of a certain amount of glycerine and absolute ethyl alcohol,
Stirring and dissolving obtains orange solution；
Step 2：The orange solution that step 1 obtains is transferred in 50ml water heating kettles at 160~200 DEG C and reacts 12~24
Hour, then washed, centrifugation, 60 DEG C of drying obtain the di-iron trioxide material of light red；
Step 3：The di-iron trioxide material obtained in 0.075g step 2 is weighed, is dissolved in 100ml absolute ethyl alcohols, then
Appropriate a concentration of 28% ammonia spirit is added, then the solution of tetrabutyl titanate of certain volume is slowly added dropwise in ultrasound 15 minutes；
Step 4：The mixed solution that step 3 is obtained in 45 DEG C of water-baths 12~36 hours, then washing, centrifuge,
60 DEG C are dried to obtain unformed coated by titanium dioxide di-iron trioxide material；
Step 5：It is small that the di-iron trioxide material that step 4 obtains is warming up to 400~800 DEG C of heat preservations 3~6 in air atmosphere
When, it is cooled to room temperature, obtains final coated by titanium dioxide di-iron trioxide composite negative pole material.
2. preparation method according to claim 1, it is characterised in that：In the step 1 iron concentration be 0.02~
0.10mol/L。
3. preparation method according to claim 1, it is characterised in that：The body of glycerine and absolute ethyl alcohol in the step 1
Product is than control 1:1~8.
4. preparation method according to claim 1, it is characterised in that：Butyl titanate and absolute ethyl alcohol in the step 3
Volume ratio be 0.6~1.2：100.
5. preparation method according to claim 1, it is characterised in that：Ammonia spirit and absolute ethyl alcohol in the step 3
Volume ratio is 0.2~0.5：100.
6. according to the application of any coated by titanium dioxide ferric oxide composite materials of claim 1-5, which is characterized in that
The coated by titanium dioxide ferric oxide composite material obtained and acetylene black, PVDF, in mass ratio 8:1:1 is mixed,
Slurry is made, is coated uniformly on copper foil, circular electrode pole piece is stamped into after 24 hours through 120 DEG C of vacuum dryings.
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