CN108417786A - A kind of rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method - Google Patents
A kind of rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method Download PDFInfo
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- CN108417786A CN108417786A CN201810033948.5A CN201810033948A CN108417786A CN 108417786 A CN108417786 A CN 108417786A CN 201810033948 A CN201810033948 A CN 201810033948A CN 108417786 A CN108417786 A CN 108417786A
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- oxalic acid
- ferrous
- lithium ion
- ferrous oxalate
- ion battery
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- 229940062993 ferrous oxalate Drugs 0.000 title claims abstract description 68
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 158
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 52
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 43
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 43
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 43
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 9
- 238000003483 aging Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910000904 FeC2O4 Inorganic materials 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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 rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation methods, belong to technical field of lithium ion battery negative.Ferrous sulfate is added in deionized water solution, stirring is to being completely dissolved to obtain ferrous sulfate solution；Deionized water and ethyl alcohol are configured to mixed liquor, solid oxalic acid is then added into mixed liquor stirs the oxalic acid solution that water white transparency is obtained to being completely dissolved；The ferrous sulfate solution that will be obtained is added oxalic acid solution by peristaltic pump, obtains yellow suspension；Obtained yellow suspension is aged 0.5~4h under the conditions of 10 DEG C ~ 60 DEG C, is filtered, washed and dried after the completion of ageing, obtains ferrous oxalate dihydrate light yellow product；Under argon gas or nitrogen inert atmosphere, obtained ferrous oxalate dihydrate is obtained into rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material in sintering.The present invention in order to overcome in the prior art ferrous oxalate material conductivity is low caused by pattern is bad, cycle performance is bad the problems such as.
Description
Technical field
The present invention relates to a kind of rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, belong to lithium from
Sub- cell negative electrode material technical field.
Background technology
Since 1991 Sony Corporation of Japan release commercial li-ion battery since, lithium ion battery be widely used in mobile phone,
The fields such as notebook, charger baby, electric vehicle.But existing material system be difficult to meet mancarried electronic aid, electric vehicle and
The application requirements higher and higher to energy density such as extensive energy stores.Therefore, exploitation energy density height, good cycle,
The battery material of safety and stability becomes the new direction of current lithium cell negative pole material development.
Currently, the research of lithium ion battery negative material is broadly divided into according to the reaction mechanism of material：Plug-in type type（Stone
Ink, TiO2、Li4Ti5O12）, alloying type（Si, Sn, Al etc.）With conversion reaction type（FeO, NiO, CoO etc.）.And conversion reaction type
Negative material mainly using transition metal oxide as representative, be easier on this basis prepare transition metal oxysalt also by with
Do lithium ion battery negative material.Tirado seminars of Cordoba university of Spain synthesize and report oxalic acid for the first time within 2008
Ferrous performance as lithium ion battery negative material simultaneously studies the conversion process of charge and discharge process mesoxalic acid ferrous iron.
2011, Ta Mentong, electric vehicle crossed cobalt doped and synthesize to have obtained FexCo1-xC2O4Composite material, and characterize its electrochemistry
Can, in cobalt doped x=0.25, cycle performance and the high rate performance for obtaining material are best.Nanyang Technological University in 2012
The ferrous oxalate of two kinds of appearance structures has been prepared by using different solvents for Madhvi seminars --- silk cocoon shape and bar
Shape carries out electrochemical property test to the ferrous oxalate of two kinds of patterns, and to the deintercalation process of lithium ion in charge and discharge process and
Electrode reaction is studied, they point out that the appearance structure of ferrous oxalate has very its chemical property especially high rate performance
Big influence.Since the conductivity of ferrous oxalate is low, the shortcomings of lithium ion diffusion rate is slow, cause following for the first time for its negative material
Ring is less efficient, and capacity attenuation is very fast.
Invention content
Ferrous oxalate material conductivity caused by pattern is bad is low, cycle performance in order to overcome in the prior art by the present invention
The problems such as bad, the present invention provide a kind of rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method.This hair
It is bright to be achieved through the following technical solutions.
A kind of rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, is as follows：
Ferrous sulfate is added in deionized water solution by step 1, and it is 5% ~ 25% to stir to being completely dissolved to obtain mass fraction
Ferrous sulfate solution；
Deionized water and ethyl alcohol according to volume ratio are 1 ~ 9 by step 2:9 ~ 1 are configured to mixed liquor, are then added into mixed liquor
Solid oxalic acid stirs the oxalic acid solution that water white transparency is obtained to being completely dissolved；
Step is added by peristaltic pump under the conditions of temperature is 10 DEG C ~ 60 DEG C in step 3, the ferrous sulfate solution for obtaining step 1
2 obtained oxalic acid solutions, control are added the time as 10min ~ 30min, obtain yellow suspension；
Step 4, the yellow suspension for obtaining step 3 are aged 0.5~4h under the conditions of 10 DEG C ~ 60 DEG C, filtered after the completion of ageing,
Washing and drying, obtain ferrous oxalate dihydrate light yellow product；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered at 120 DEG C ~ 200 DEG C
4 ~ 10h obtains rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
Solid oxalic acid is 1 according to the molar ratio of oxalic acid and ferrous sulfate in the step 2:1~3:1 is added.
The volume ratio of ferrous sulfate solution and oxalic acid solution is 9 ~ 45 in the step 3:10~20.
The beneficial effects of the invention are as follows：
Using environmentally friendly green public good technique, rodlike multi-layer microporous ferrous oxalate powder has been prepared by liquid-phase precipitation method
Body material, shape characteristic are conducive to the transmission and electron transfer of lithium ion in charge and discharge process, hence it is evident that improve the electricity of material
The chemical properties such as performance and cycle are led, its application in field of lithium ion battery is promoted.
Description of the drawings
Fig. 1 is flow diagram of the present invention.
Fig. 2 is the x-ray diffraction pattern of rodlike multi-layer microporous ferrous oxalate prepared by the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope of the rodlike multi-layer microporous ferrous oxalate containing the crystallization water prepared by present example 2-4.
Wherein（a）（d）For embodiment 2；（b）（e）For embodiment 3；（c）（f）For embodiment 4.
Fig. 4 is the transmission electron microscope picture of rodlike multi-layer microporous ferrous oxalate prepared by present example 4.
Fig. 5 is the circulation figure of rodlike multi-layer microporous ferrous oxalate prepared by present example 4.
Fig. 6 is the charge and discharge cycles figure of rodlike multi-layer microporous ferrous oxalate prepared by present example 4.
Specific implementation mode
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Figure 1, the rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, specific steps are such as
Under：
10mmol ferrous sulfate is added in 45mL deionized water solutions by step 1, and 15min is to being completely dissolved to obtain matter for stirring
Measure the ferrous sulfate solution that score is 5%；
Deionized water and ethyl alcohol according to volume ratio are 3 by step 2:2 are configured to 12mL mixed liquors, are then added into mixed liquor
Solid oxalic acid electromagnetic agitation 30min obtains the oxalic acid solution of water white transparency to being completely dissolved；Wherein solid oxalic acid according to oxalic acid with
The molar ratio of ferrous sulfate is 1:1 is added；
Step 3, the ferrous sulfate solution for obtaining step 1 are obtained under the conditions of temperature is 30 DEG C by peristaltic pump addition step 2
Oxalic acid solution, it is 15min that control, which is added the time, and stir speed (S.S.) 2300r/min obtains yellow suspension；Ferrous sulfate solution
Volume ratio with oxalic acid solution is 45:12；
The yellow suspension that step 3 obtains is aged 1h by step 4 under the conditions of 30 DEG C, is filtered, washed and is done after the completion of ageing
It is dry, obtain ferrous oxalate dihydrate light yellow product（FeC2O4·2H2O, rodlike multi-layer microporous ferrous oxalate containing the crystallization water）；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered 8h at 150 DEG C, is obtained
To rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
The rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material x-ray diffraction pattern that the present embodiment is prepared
As shown in Fig. 2, it is ferrous oxalate that as can be seen from Figure 2 lithium ion battery negative material, which is prepared, in the present embodiment.
Embodiment 2
As shown in Figure 1, the rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, specific steps are such as
Under：
10mmol ferrous sulfate is added in 45mL deionized water solutions by step 1, and 15min is to being completely dissolved to obtain matter for stirring
Measure the ferrous sulfate solution that score is 5%；
Deionized water and ethyl alcohol according to volume ratio are 3 by step 2:2 are configured to 12mL mixed liquors, are then added into mixed liquor
Solid oxalic acid electromagnetic agitation 30min obtains the oxalic acid solution of water white transparency to being completely dissolved；Wherein solid oxalic acid according to oxalic acid with
The molar ratio of ferrous sulfate is 1:1 is added；
Step 3, the ferrous sulfate solution for obtaining step 1 are obtained under the conditions of temperature is 30 DEG C by peristaltic pump addition step 2
Oxalic acid solution, it is 15min that control, which is added the time, and stir speed (S.S.) 2300r/min obtains yellow suspension；Ferrous sulfate solution
Volume ratio with oxalic acid solution is 45:12；
The yellow suspension that step 3 obtains is aged 1h by step 4 under the conditions of 30 DEG C, is filtered, washed and is done after the completion of ageing
It is dry, obtain ferrous oxalate dihydrate light yellow product（FeC2O4·2H2O, rodlike multi-layer microporous ferrous oxalate containing the crystallization water）；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered 8h at 170 DEG C, is obtained
To rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
The rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material scanning electron microscope (SEM) photograph that the present embodiment is prepared is such as
Fig. 3（a）（d）It is shown, from Fig. 3（a）（d）In be apparent that ferrous oxalate lithium ion battery negative material lamellar structure and
Rod-like shape.
Embodiment 3
As shown in Figure 1, the rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, specific steps are such as
Under：
10mmol ferrous sulfate is added in 45mL deionized water solutions by step 1, and 15min is to being completely dissolved to obtain matter for stirring
Measure the ferrous sulfate solution that score is 5%；
Deionized water and ethyl alcohol according to volume ratio are 1 by step 2:4 are configured to 12mL mixed liquors, are then added into mixed liquor
Solid oxalic acid electromagnetic agitation 30min obtains the oxalic acid solution of water white transparency to being completely dissolved；Wherein solid oxalic acid according to oxalic acid with
The molar ratio of ferrous sulfate is 1:1 is added；
Step 3, the ferrous sulfate solution for obtaining step 1 are obtained under the conditions of temperature is 30 DEG C by peristaltic pump addition step 2
Oxalic acid solution, it is 15min that control, which is added the time, and stir speed (S.S.) 2300r/min obtains yellow suspension；Ferrous sulfate solution
Volume ratio with oxalic acid solution is 45:12；
The yellow suspension that step 3 obtains is aged 1h by step 4 under the conditions of 30 DEG C, is filtered, washed and is done after the completion of ageing
It is dry, obtain ferrous oxalate dihydrate light yellow product（FeC2O4·2H2O, rodlike multi-layer microporous ferrous oxalate containing the crystallization water）；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered 8h at 150 DEG C, is obtained
To rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
The rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material scanning electron microscope (SEM) photograph that the present embodiment is prepared is such as
Fig. 3（b）（e）It is shown, from Fig. 3（b）（e）In be apparent that ferrous oxalate lithium ion battery negative material lamellar structure and
Rod-like shape.
Embodiment 4
As shown in Figure 1, the rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, specific steps are such as
Under：
10mmol ferrous sulfate is added in 45mL deionized water solutions by step 1, and 15min is to being completely dissolved to obtain matter for stirring
Measure the ferrous sulfate solution that score is 5%；
Deionized water and ethyl alcohol according to volume ratio are 1 by step 2:9 are configured to 12mL mixed liquors, are then added into mixed liquor
Solid oxalic acid electromagnetic agitation 30min obtains the oxalic acid solution of water white transparency to being completely dissolved；Wherein solid oxalic acid according to oxalic acid with
The molar ratio of ferrous sulfate is 1:1 is added；
Step 3, the ferrous sulfate solution for obtaining step 1 are obtained under the conditions of temperature is 30 DEG C by peristaltic pump addition step 2
Oxalic acid solution, it is 15min that control, which is added the time, and stir speed (S.S.) 2300r/min obtains yellow suspension；Ferrous sulfate solution
Volume ratio with oxalic acid solution is 45:12；
The yellow suspension that step 3 obtains is aged 1h by step 4 under the conditions of 30 DEG C, is filtered, washed and is done after the completion of ageing
It is dry, obtain ferrous oxalate dihydrate light yellow product（FeC2O4·2H2O, rodlike multi-layer microporous ferrous oxalate containing the crystallization water）；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered 8h at 170 DEG C, is obtained
To rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
The rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material scanning electron microscope (SEM) photograph that the present embodiment is prepared is such as
Fig. 3（c）（f）It is shown, from Fig. 3（c）（f）In be apparent that ferrous oxalate lithium ion battery negative material lamellar structure and
Rod-like shape, transmission electron microscope picture is as shown in figure 4, it is observed that nano-pore metastructure from Fig. 4.
Weigh anhydrous oxalic acid ferrous iron, 0.15g acetylene blacks, 0.05g Kynoar that 0.3g the present embodiment is prepared
（PVDF）, it is put into mortar, grinds 30min, 1mlN- N-methyl-2-2-pyrrolidone N solution is then added, continue to grind 20min, it will
On mixture of viscous form even spread and copper foil, then preliminarily dried 15min under the conditions of 80 DEG C, then the vacuum at 80 DEG C dry
Dry 12h, later rolls copper foil, then be cut into the disk of a diameter of 13.5mm in case, and pole piece is made.
In the glove box full of argon gas（O2Content 1ppm, water content 1ppm）, in conventional manner by pole piece, diaphragm,
Lithium piece and foam nickel screen are assembled into button cell, are carried out on constant current charge-discharge system with the rate of 1C=0.22mA/cm2
Battery performance is tested, and circulation result figure is as shown in figure 5, charge and discharge cycles figure is as shown in Figure 6.
Embodiment 5
As shown in Figure 1, the rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, specific steps are such as
Under：
Ferrous sulfate is added in 9mL deionized water solutions by step 1, and stirring 15min is to being completely dissolved to obtain mass fraction
25% ferrous sulfate solution；
Deionized water and ethyl alcohol according to volume ratio are 9 by step 2:1 is configured to 20mL mixed liquors, is then added into mixed liquor
Solid oxalic acid electromagnetic agitation 30min obtains the oxalic acid solution of water white transparency to being completely dissolved；Wherein solid oxalic acid according to oxalic acid with
The molar ratio of ferrous sulfate is 3:1 is added；
Step 3, the ferrous sulfate solution for obtaining step 1 are obtained under the conditions of temperature is 10 DEG C by peristaltic pump addition step 2
Oxalic acid solution, it is 30min that control, which is added the time, and stir speed (S.S.) 2300r/min obtains yellow suspension；Ferrous sulfate solution
Volume ratio with oxalic acid solution is 9:20；
The yellow suspension that step 3 obtains is aged 4h by step 4 under the conditions of 10 DEG C, is filtered, washed and is done after the completion of ageing
It is dry, obtain ferrous oxalate dihydrate light yellow product（FeC2O4·2H2O, rodlike multi-layer microporous ferrous oxalate containing the crystallization water）；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered 10h at 120 DEG C, is obtained
To rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
Embodiment 6
As shown in Figure 1, the rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, specific steps are such as
Under：
Ferrous sulfate is added in 20mL deionized water solutions by step 1, and 15min is to being completely dissolved to obtain mass fraction for stirring
For 15% ferrous sulfate solution；
Deionized water and ethyl alcohol according to volume ratio are 9 by step 2:1 is configured to 10mL mixed liquors, is then added into mixed liquor
Solid oxalic acid electromagnetic agitation 30min obtains the oxalic acid solution of water white transparency to being completely dissolved；Wherein solid oxalic acid according to oxalic acid with
The molar ratio of ferrous sulfate is 2:1 is added；
Step 3, the ferrous sulfate solution for obtaining step 1 are obtained under the conditions of temperature is 60 DEG C by peristaltic pump addition step 2
Oxalic acid solution, it is 10min that control, which is added the time, and stir speed (S.S.) 2300r/min obtains yellow suspension；Ferrous sulfate solution
Volume ratio with oxalic acid solution is 20:10；
The yellow suspension that step 3 obtains is aged 0.5h by step 4 under the conditions of 60 DEG C, is filtered, washed and is done after the completion of ageing
It is dry, obtain ferrous oxalate dihydrate light yellow product（FeC2O4·2H2O, rodlike multi-layer microporous ferrous oxalate containing the crystallization water）；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered 4h at 200 DEG C, is obtained
To rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
The specific implementation mode of the present invention is explained in detail above in association with attached drawing, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (3)
1. a kind of rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method, it is characterised in that specific steps are such as
Under：
Ferrous sulfate is added in deionized water solution by step 1, and it is 5% ~ 25% to stir to being completely dissolved to obtain mass fraction
Ferrous sulfate solution；
Deionized water and ethyl alcohol according to volume ratio are 1 ~ 9 by step 2:9 ~ 1 are configured to mixed liquor, are then added into mixed liquor
Solid oxalic acid stirs the oxalic acid solution that water white transparency is obtained to being completely dissolved；
Step is added by peristaltic pump under the conditions of temperature is 10 DEG C ~ 60 DEG C in step 3, the ferrous sulfate solution for obtaining step 1
2 obtained oxalic acid solutions, control are added the time as 10min ~ 30min, obtain yellow suspension；
Step 4, the yellow suspension for obtaining step 3 are aged 0.5~4h under the conditions of 10 DEG C ~ 60 DEG C, filtered after the completion of ageing,
Washing and drying, obtain ferrous oxalate dihydrate light yellow product；
Step 5, under argon gas or nitrogen inert atmosphere, the ferrous oxalate dihydrate that step 4 obtains is sintered at 120 DEG C ~ 200 DEG C
4 ~ 10h obtains rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material.
2. rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method according to claim 1, special
Sign is：Solid oxalic acid is 1 according to the molar ratio of oxalic acid and ferrous sulfate in the step 2:1~3:1 is added.
3. rodlike multi-layer microporous ferrous oxalate lithium ion battery negative material preparation method according to claim 1, special
Sign is：The volume ratio of ferrous sulfate solution and oxalic acid solution is 9 ~ 45 in the step 3: 10~20.
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| CN111135863A (en) * | 2019-12-30 | 2020-05-12 | 肇庆学院 | FeC2O4·2H2O nanorod photo-Fenton catalyst, preparation method and application thereof |
| CN111304687A (en) * | 2020-03-31 | 2020-06-19 | 上海应用技术大学 | Method for synthesizing rod-shaped ferrous oxalate |
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| CN112490432A (en) * | 2020-12-16 | 2021-03-12 | 昆明理工大学 | Germanium-doped ferrous oxalate lithium ion battery composite negative electrode material and preparation method thereof |
| CN113979859A (en) * | 2021-09-16 | 2022-01-28 | 昆明理工大学 | Preparation method of ordered three-dimensional framework structure metal oxalate lithium ion battery negative electrode material |
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| CN111304687B (en) * | 2020-03-31 | 2022-04-05 | 上海应用技术大学 | Method for synthesizing rod-shaped ferrous oxalate |
| CN112490432A (en) * | 2020-12-16 | 2021-03-12 | 昆明理工大学 | Germanium-doped ferrous oxalate lithium ion battery composite negative electrode material and preparation method thereof |
| CN113979859A (en) * | 2021-09-16 | 2022-01-28 | 昆明理工大学 | Preparation method of ordered three-dimensional framework structure metal oxalate lithium ion battery negative electrode material |
| WO2023040406A1 (en) * | 2021-09-16 | 2023-03-23 | 昆明理工大学 | Preparation method for metal oxalate lithium ion battery negative electrode material with ordered three-dimensional skeleton structure |
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