CN104766953B - Preparation method of titanium dioxide/iron oxide composite anode material - Google Patents
Preparation method of titanium dioxide/iron oxide composite anode material Download PDFInfo
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- CN104766953B CN104766953B CN201510149172.XA CN201510149172A CN104766953B CN 104766953 B CN104766953 B CN 104766953B CN 201510149172 A CN201510149172 A CN 201510149172A CN 104766953 B CN104766953 B CN 104766953B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title abstract description 18
- 239000010405 anode material Substances 0.000 title abstract 4
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a titanium dioxide/iron oxide composite anode material. The preparation method sequentially comprises the following steps of (1) dissolving titanyl sulfate into deionized water, then, adding iron salt, and stirring until the iron salt is dissolved; (2) adding polyvinylpyrrolidone into the solution obtained in the step (1), and stirring until polyvinylpyrrolidone is completely dissolved; (3) dropwise adding methanamide into the solution obtained in the step (2) while fiercely stirring, and aging gel after stirring for 5-10 minutes; (4) drying the gel obtained in the step (3) under normal pressure at 50-70 DEG C for 22-26 hours to obtain a precursor product; and (5) heating the precursor product at the air atmosphere to 500-800 DEG C, keeping the temperature for 5-7 hours, and cooling to the room temperature to obtain the titanium dioxide/iron oxide composite anode material. The titanium dioxide/iron oxide composite anode material has relatively-high specific capacity and stable circulating performance.
Description
Technical field
The invention belongs to lithium ion battery new energy Material Field is and in particular to a kind of titanium dioxide/ferrum oxide composite negative pole
The preparation method of material.
Background technology
Lithium ion battery is widely used in mobile phone, video camera and computer etc. as a kind of novel green high-energy chemistry power supply
All kinds of Miniature Portable Units, also have important application prospect in fields such as electric automobile, Aero-Space simultaneously.In recent years, with
Electric automobile is that the new industrial technology of representative is developed rapidly, meanwhile also lithium ion battery is proposed higher
Performance requirement.Negative material is main ingredient in lithium ion battery, and current commercial Li-ion battery typically adopts stone
As negative material, its storage lithium specific capacity is typically smaller than 350mah g to black sill-1, this relatively low specific capacity be increasingly difficult to
Meet actual demand.In addition, the intercalation potential of this graphite-based negative material is close with lithium metal, in charge and discharge process easily
Li dendrite occurs, leads to battery short circuit, thus safety problem occurs.Therefore, research and development Novel high-specific capacity flexible and safety
More preferable negative material is important all the more.
Titanic oxide material is considered as a kind of excellent negative material, the removal lithium embedded voltage of its anatase titanium dioxide
Platform, in 1.75v, effectively avoids the generation of Li dendrite, improves the use safety of battery.In addition its titanyl is formed
Octahedral structure, this structure change in volume in charge and discharge process is smaller so that cycle performance is more stable.But, to the greatest extent
The theoretical specific capacity of pipe titanium dioxide reaches 335mah g-1, but typically every mole of titanium dioxide is only capable of reality in actual use
The lithium of existing 0.5 mole of deintercalation, specific capacity is about 168mah g-1, relatively low specific capacity also largely limit its actual should
With.
In recent years, there is the transition metal oxide of higher theoretical specific capacity (as fe2o3、co3o4Deng) be subject to get more and more
Concern.As fe2o3Lithium storage content be up to about 1008mah g-1, close to 3 times of conventional graphite base cathode specific capacity.For
This, by fe2o3Material and titanic oxide material carry out compound can be with effectively utilizes fe2o3Height ratio capacity and titanium dioxide steady
Fixed cycle performance, the composite obtaining has higher specific capacity and excellent cycle performance.
Existing fe at present2o3Material and titanic oxide material carry out compound preparation method, mainly pass through hydro-thermal method or change
Learn sedimentation method synthesis one of which material (fe2o3Or titanium dioxide), then carry out another material of load of next step again
(titanium dioxide or fe2o3), finally obtain fe2o3With the composite of titanium dioxide, this method and step is loaded down with trivial details, period ratio
Longer, energy consumption is big, is unfavorable for large-scale production, yet there are no report one-step method fe2o3Material and composite titania material.
At present for fe2o3With the composite of titanium dioxide, yet there are no the patent report for lithium ion battery.Application
Number a kind of iron oxide sensitized lamellar titanium oxide visible light catalyst and preparation side are reported for 200510023961.5 patent
Method.Lou et al. (yu l, wang z, zhang l, et al.tio2nanotube arrays grafted with
fe2o3hollow nanorods as integrated electrodes for lithium-ion batteries[j]
.journal of materials chemistry a, 2013,1 (1): 122-127.) fe is first synthesized by coprecipitation2o3Empty
Heart pipe, then carries out, in outer layer, the fe that carried titanium dioxide synthesizes hollow2o3/ composite titania material, it is in 0.05～3.0v
Charging/discharging voltage interval in, its first charge-discharge capacity is respectively 750mah g-1With 600mah g-1, in 100ma cm-2Electricity
Under current density, 50 its reversible capacities of circulation are 395mah g-1.Guo et al. (zhang, x.；chen,h.x.；xie,y.p.；
guo,j.x.,ultralong life lithium-ion battery anode with superior high-rate
capability and excellent cyclic stability from mesoporous fe2o3@tio2core-shell
Nanorods.journal of materials chemistry a 2014,2 (11), 3912-3918.) combine hydro-thermal method and
Chemical precipitation method first synthesizes feooh/tio2Presoma, then calcining obtains the fe with nucleocapsid structure2o3/tio2Composite,
As lithium ion battery negative material, carry out electrochemical property test in charging/discharging voltage interval for 0.01～3.0v, it is first
Discharge capacity is 1223mah g-1, initial charge capacity is 792mah g-1.In 0.1a g-1Under electric current density circulation 50 times its can
Inverse capacity is 450mah g-1.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of titanium dioxide/ferrum oxide composite negative pole of stable cycle performance
The preparation method of material.
In order to solve above-mentioned technical problem, the present invention provides a kind of preparation of titanium dioxide/ferrum oxide composite negative pole material
Method, is characterized in that comprising the following steps successively:
1) 1.39 × 10, are weighed-3～2.71 × 10-3The titanyl sulfate of mol is dissolved in deionized water, is subsequently adding ferrum
Salt, stirring, until iron salt dissolved, obtains solution (for orange solution)；
Titanium and fe3+Mol ratio is 1.0～2.0:1；
2), to step 1) add 0.2～0.3 gram of Polyvinylpyrrolidone in the solution of gained, stir to polyvinyl pyrrole
Alkanone is completely dissolved；
3), with vigorous stirring, to step 2) in 0.5～1.0 milliliter of solution Deca (about 0.5～1 minute completion of dropping)
Methanamide, stirring 5～10 minutes after, carry out aged gel 2～3 hours in 50～70 DEG C (preferably 60 DEG C)；
4), by step 3) gained gel under 50～70 DEG C of normal pressure (preferably 60 DEG C) be dried 22～26 hours (preferably
24 hours), obtain precursor product；
5), by step 4) precursor product of gained is warming up to 500～800 DEG C in air atmosphere and is incubated 5～7 hours,
It is cooled to room temperature, obtain titanium dioxide/ferrum oxide composite negative pole material.
The improvement of the preparation method of the titanium dioxide as the present invention/ferrum oxide composite negative pole material: described step 1) in
Iron salt is ferric nitrate, high iron chloride or iron sulfate.
The improvement further of the preparation method of the titanium dioxide as the present invention/ferrum oxide composite negative pole material: described step
In rapid 1), the mol ratio of deionized water and titanyl sulfate is 78～120:1 (preferably 79～90:1).
The improvement further of the preparation method of the titanium dioxide as the present invention/ferrum oxide composite negative pole material: described step
In rapid 2), polyvinylpyrrolidonemolecules molecules amount is 10000～130000.
The improvement further of the preparation method of the titanium dioxide as the present invention/ferrum oxide composite negative pole material:
Described step 1) in, iron salt is high iron chloride, titanium and fe3+Mol ratio is 1～1.5:1 (more preferably 1～1.35:1)；
Described step 2) in, the amount of Polyvinylpyrrolidone is 0.25～0.3 gram；
Described step 5) in, it is incubated 5 hours in 600 DEG C.
In the present invention, be stirred vigorously and refer to 800～1000 rev/min, remaining stirring rotating speed be 600～800 turns/
Per minute.
The present invention first adopts sol-gal process one-step synthesis titanium dioxide and the precursor product of ferric oxide composite material to do
Gel, after after heat treatment obtain titanium dioxide and ferrum oxide composite negative pole material.Preparation condition of the present invention is simply gentle, equipment
Require low, process route is simple, is easy to large-scale production.Obtained titanium dioxide/ferrum oxide composite negative pole material has relatively
High specific capacity and stable cycle performance.Titanium dioxide of the present invention/ferrum oxide composite negative pole material has higher discharge and recharge
Capacity and more stable cycle performance are (in 0.1a g-1Circulate 50 its reversible capacities gram under electric current density and remain 930mah g-1).
The present invention adopts sol-gal process one-step synthesis fe2o3With the presoma of composite titania material, at calcining
Reason fabricated in situ fe2o3With the composite of titanium dioxide, this preparation method is simple, cycle is short, cheap it is adaptable to big
Large-scale production.
Brief description
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail:
Fig. 1 is the xrd figure of the titanium dioxide/ferrum oxide composite negative pole material of embodiment 1 preparation.
Fig. 2 is the xrd figure of the titanium dioxide/ferrum oxide composite negative pole material of embodiment 2 preparation.
Fig. 3 is 500 times of scanning electron microscopic picture of the titanium dioxide/ferrum oxide composite negative pole material of embodiment 3 preparation.
Fig. 4 is 3000 times of scanning electron microscopic picture of the titanium dioxide/ferrum oxide composite negative pole material of embodiment 5 preparation.
Fig. 5 be embodiment 1 preparation titanium dioxide/ferrum oxide composite negative pole material cycle performance figure.
Fig. 6 be embodiment 2 preparation titanium dioxide/ferrum oxide composite negative pole material cycle performance figure.
Fig. 7 be embodiment 3 preparation titanium dioxide/ferrum oxide composite negative pole material cycle performance figure.
Fig. 8 be embodiment 4 preparation titanium dioxide/ferrum oxide composite negative pole material cycle performance figure.
Fig. 9 be embodiment 5 preparation titanium dioxide/ferrum oxide composite negative pole material cycle performance figure.
Specific embodiment
The molecular weight of the Polyvinylpyrrolidone used in following case is 10000-130000.It is stirred vigorously and refer to 800
～1000 rev/min, the rotating speed of remaining stirring is 600～800 rev/min.
Embodiment 1, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.36 gram (1.39 × 10-3Mol) titanyl sulfate, is dissolved in 2 ml deionized water (0.11mol), after
Add 0.37 gram (1.37 × 10-3Mol) high iron chloride, stir the orange-yellow solution of formation；
2), to step 1) solution of gained adds 0.25 gram of Polyvinylpyrrolidone to stir to be completely dissolved to it；
3), under intense agitation, to step 2) it is slowly added dropwise 0.5 milliliter of Methanamide (that is, about half point in resulting solution
Clock drips off), stirring 5 minutes after at 60 DEG C aged gel 3 hours；
4), by step 3) gained gel is dried 24 hours at 60 DEG C of normal pressure, obtains precursor product；
5), the precursor product of gained is warming up to 600 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material (powder body).
Experiment 1, the titanium dioxide/ferric oxide composite material by being obtained, acetylene black and pvdf (Kynoar) are with quality
Mixed than for 8:1:1, be dispersed in nmp (n- methyl pyrrolidone) that (described nmp is the 20-39 of above-mentioned 3 weight sums
Times)；Make slurry, be coated uniformly on Copper Foil, (coating layer thickness is 0.1- to be stamped into circular electrode pole piece after vacuum drying
0.5mm), it is to electrode with metal lithium sheet, 1mol/l lipf6/dmc+ec (volume ratio is 1:1) is electrolyte,
Celgard2300 is barrier film, is assembled into button cell and carries out electro-chemical test, and its charging/discharging voltage scope is 0.01～3.0v.
In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 930mah g-1, its first discharge capacity be 1215mah g-1,
Charging capacity is 843mah g-1.
Embodiment 2, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.36 gram (1.39 × 10-3Mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after
Add 0.5 gram (1.85 × 10-3Mol) high iron chloride, stir formation orange solution；
2), to step 1) solution of gained adds 0.25 gram of Polyvinylpyrrolidone to stir to be completely dissolved to it,
3), under intense agitation, to step 2) it is slowly added dropwise 0.5 milliliter of Methanamide (about half a minute in resulting solution
Drip off), stirring carries out aged gel 3 hours after 5 minutes at 60 DEG C；
4), by step 3) gained gel is dried 24 hours at 60 DEG C of normal pressure, obtains precursor product；
5), the precursor product of gained is warming up to 600 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material (powder body).
By the titanium dioxide/ferric oxide composite material being obtained as experiment 1 is detected, its charging/discharging voltage scope is
0.01～3.0v.In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 952mah g-1, its first discharge capacity be
1421mah g-1, charging capacity is 983mah g-1.
Embodiment 3, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.7 gram (2.71 × 10-3Mol) titanyl sulfate, is dissolved in 4 milliliters of (0.22mol) deionized waters, after
Add 0.37 gram (1.37 × 10-3Mol) high iron chloride, stir formation orange solution；
2), to step 1) solution of gained adds 0.25 gram of Polyvinylpyrrolidone to stir to be completely dissolved to it；
3), under intense agitation to step 2) (about half a minute drips to be slowly added dropwise 0.5 milliliter of Methanamide in resulting solution
Complete), stirring carries out aged gel 3 hours after 5 minutes at 60 DEG C；
4), by step 3) drying at 60 DEG C of normal pressure of gained gel obtains precursor product in 24 hours；
5), the precursor product of gained is warming up to 600 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material powder body.
By the titanium dioxide/ferric oxide composite material being obtained as experiment 1 is detected, its charging/discharging voltage scope is
0.01～3.0v.In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 285mah g-1, its first discharge capacity be
1291mah g-1, charging capacity is 862mah g-1.
Embodiment 4, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.7 gram (2.71 × 10-3Mol) titanyl sulfate, is dissolved in 4 milliliters of (0.22mol) deionized waters, after
Add 0.5 gram (1.85 × 10-3Mol) high iron chloride, stir formation orange solution；
2), to step 1) add 0.25 gram of Polyvinylpyrrolidone to stir in the solution of gained to be completely dissolved to it；
3), under intense agitation to step 2) (about half a minute drips to be slowly added dropwise 0.5 milliliter of Methanamide in resulting solution
Complete), stirring carries out aged gel 3 hours after 5 minutes at 60 DEG C；
4), by step 3) drying at 60 DEG C of normal pressure of gained gel obtains precursor product in 24 hours；
5), the precursor product of gained is warming up to 600 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material powder body.
By the titanium dioxide/ferric oxide composite material being obtained as experiment 1 is detected, its charging/discharging voltage scope is
0.01～3.0v.In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 589mah g-1, its first discharge capacity be
1124mah g-1, charging capacity is 867mah g-1.
Embodiment 5, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.36 gram (1.39 × 10-3Mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after
Add 0.37 gram (1.37 × 10-3Mol) high iron chloride, stir formation orange solution；
2), to step 1) solution of gained adds 0.2 gram of Polyvinylpyrrolidone to stir to be completely dissolved to it；
3), under intense agitation to step 2) (about half a minute drips to be slowly added dropwise 0.5 milliliter of Methanamide in resulting solution
Complete), stirring carries out aged gel 3 hours after 5 minutes at 60 DEG C；
4), by step 3) gained gel is dried 24 hours at 60 DEG C of normal pressure, obtains precursor product；
5), the precursor product of gained is warming up to 600 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material powder body.
By the titanium dioxide/ferric oxide composite material being obtained as experiment 1 is detected, its charging/discharging voltage scope is
0.01～3.0v.In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 731mah g-1, its first discharge capacity be
1108mah g-1, charging capacity is 845mah g-1.
Embodiment 6, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.36 gram (1.39 × 10-3Mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after
Add 0.37 gram (1.37 × 10-3Mol) high iron chloride, stir formation orange solution；
2), to step 1) add 0.25 gram of Polyvinylpyrrolidone to stir in the solution of gained to be completely dissolved to it；
3), under intense agitation to step 2) (about half a minute drips to be slowly added dropwise 0.5 milliliter of Methanamide in resulting solution
Complete), stirring carries out aged gel 3 hours after 5 minutes at 60 DEG C；
4), by step 3) drying at 60 DEG C of normal pressure of gained gel obtains precursor product in 24 hours；
5), the precursor product of gained is warming up to 800 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material powder body.
By the titanium dioxide/ferric oxide composite material being obtained as experiment 1 is detected, its charging/discharging voltage scope is
0.01～3.0v.In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 534mah g-1, its first discharge capacity be
1084mah g-1, charging capacity is 862mah g-1.
Embodiment 7, a kind of preparation method of titanium dioxide/ferrum oxide composite negative pole material, follow the steps below successively:
1), weigh 0.36 gram (1.39 × 10-3Mol) titanyl sulfate, is dissolved in 2 milliliters of (0.11mol) deionized waters, after
Add 0.37 gram (1.37 × 10-3Mol) high iron chloride, stir formation orange solution；
2), to step 1) add 0.3 gram of Polyvinylpyrrolidone to stir in the solution of gained to be completely dissolved to it；
3), under intense agitation to step 2) (about half a minute drips to be slowly added dropwise 0.5 milliliter of Methanamide in resulting solution
Complete), stirring carries out aged gel 3 hours after 5 minutes at 60 DEG C；
4), by step 3) gained gel is dried 24 hours at 60 DEG C of normal pressure, obtains precursor product；
5), the precursor product of gained is warming up to 600 DEG C in air atmosphere and is incubated 5 hours, be cooled to room temperature, obtain
Titanium dioxide/ferrum oxide composite negative pole material powder body.
By the titanium dioxide/ferric oxide composite material being obtained as experiment 1 is detected, its charging/discharging voltage scope is
0.01～3.0v.In 0.1a g-1After circulating 50 times, its reversible capacity is still maintained at 647mah g-1, its first discharge capacity be
1126mah g-1, charging capacity is 883mah g-1.
Last in addition it is also necessary to it is noted that listed above be only the present invention several specific embodiments.Obviously, this
Bright be not limited to above example, can also have many deformation.Those of ordinary skill in the art can be from present disclosure
The all deformation directly derived or associate, are all considered as protection scope of the present invention.
Claims (5)
1. the preparation method of titanium dioxide/ferrum oxide composite negative pole material, is characterized in that comprising the following steps successively:
1) 1.39 × 10, are weighed-3～2.71 × 10-3The titanyl sulfate of mol is dissolved in deionized water, is subsequently adding iron salt, stirs
Mix until iron salt dissolved, obtain solution；
Titanium and fe3+Mol ratio is 1.0～2.0:1；
2), to step 1) add 0.2～0.3 gram of Polyvinylpyrrolidone in the solution of gained, stir to Polyvinylpyrrolidone
It is completely dissolved；
3), with vigorous stirring, to step 2) in 0.5～1.0 milliliter of solution Deca Methanamide, stirring 5～10 minutes after, in
50～70 DEG C carry out aged gel 2～3 hours；
4), by step 3) gained gel is dried 22～26 hours at 50～70 DEG C of normal pressure, obtains precursor product；
5), by step 4) precursor product of gained is warming up to 500～800 DEG C in air atmosphere and is incubated 5～7 hours, cooling
To room temperature, obtain titanium dioxide/ferrum oxide composite negative pole material.
2. titanium dioxide according to claim 1/ferrum oxide composite negative pole material preparation method it is characterised in that: institute
State step 1) in iron salt be ferric nitrate, high iron chloride or iron sulfate.
3. titanium dioxide according to claim 2/ferrum oxide composite negative pole material preparation method it is characterised in that: institute
State step 1) in deionized water and titanyl sulfate mol ratio be 78～120:1.
4. titanium dioxide according to claim 3/ferrum oxide composite negative pole material preparation method it is characterised in that: institute
State step 2) in polyvinylpyrrolidonemolecules molecules amount be 10000～130000.
5. titanium dioxide according to claim 4/ferrum oxide composite negative pole material preparation method it is characterised in that:
Described step 1) in, iron salt is high iron chloride, titanium and fe3+Mol ratio is 1～1.5:1；
Described step 2) in, the amount of Polyvinylpyrrolidone is 0.25～0.3 gram；
Described step 5) in, it is incubated 5 hours in 600 DEG C.
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| CN113793931B (en) * | 2021-11-18 | 2022-02-08 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
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| CN104241628A (en) * | 2014-09-24 | 2014-12-24 | 南京大学 | Method for preparing titanium-dioxide-modified ferric oxide microspheres as well as produced product and use of titanium-dioxide-modified ferric oxide microspheres |
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