CN108428887A - The preparation method and battery electrode material iron oxide and lithium ion battery of battery electrode material iron oxide - Google Patents
The preparation method and battery electrode material iron oxide and lithium ion battery of battery electrode material iron oxide Download PDFInfo
- Publication number
- CN108428887A CN108428887A CN201810333107.6A CN201810333107A CN108428887A CN 108428887 A CN108428887 A CN 108428887A CN 201810333107 A CN201810333107 A CN 201810333107A CN 108428887 A CN108428887 A CN 108428887A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- battery electrode
- iron oxide
- tween
- ethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of preparation method of battery electrode material iron oxide and battery electrode material iron oxide and lithium ion battery, are related to technical field of battery electrode materials.The preparation method of the battery electrode material iron oxide, mainly using trivalent iron salt as source of iron, the aqueous solution of tween/ethylene glycol is guiding growth agent, using pH adjusting agent adjusting ambient pH, the battery electrode material iron oxide with hollow rod structure is prepared by hydro-thermal method, wherein, the aqueous solution of tween/ethylene glycol is not only able to the boiling point of adjusting hydrothermal reaction, and tween forms colloid in aqueous solution, generate absorption electric double layer, adsorb iron ion guiding growth, so that the pattern of iron oxide is easier to control, the hollow rod structure of obtained iron oxide can not only provide the reaction contact area of bigger, also so that the electric conductivity of iron oxide improves, it is conducive to provide the ion transmission channel of bigger, and then improve the chemical property of material.
Description
Technical field
The present invention relates to technical field of battery electrode materials, in particular to a kind of battery electrode material iron oxide
Preparation method and battery electrode material iron oxide and lithium ion battery.
Background technology
In the critical material of manufacture battery, negative material is an important factor for determining its working performance and price.At present
Commercialized negative material is mainly graphite-like carbon material, but their theoretical capacities are only 372mAh/g, and in charge and discharge process
In " Li dendrite " formation, be easy to cause battery short circuit and cause explosion, therefore its theoretical capacity is low and safety difference limits battery
Development.
In order to which chemical properties, the various novel high energy negative materials such as the specific capacity that improves lithium ion battery are developed
Come.Wherein, iron oxide (Fe2O3) it is high because of resourceful, environmental-friendly and specific capacity the advantages that (1005mAh/g) by researcher
Extensive concern, be expected to become cell negative electrode material of new generation.Fe2O3Theoretical specific capacity is high, but poorly conductive, stable circulation
Property is not good enough, limits the commercially use of it.
In view of this, special propose the present invention.
Invention content
First of the present invention is designed to provide a kind of battery electrode material Fe2O3Preparation method, which adopts
Use trivalent iron salt as source of iron, the aqueous solution of tween/ethylene glycol is as guiding growth agent, using pH adjusting agent adjusting ambient pH,
The battery electrode material Fe with hollow rod structure is prepared by hydro-thermal method2O3, battery electrode material Fe2O3With good
Electric conductivity and the chemical properties such as cyclical stability.
Second object of the present invention is to provide a kind of battery electrode material Fe2O3, the Fe2O3With hollow rod structure.
Third object of the present invention is to provide a kind of lithium ion battery, including above-mentioned battery electrode material Fe2O3。
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
The present invention provides a kind of battery electrode material Fe2O3Preparation method, include the following steps：
(a) trivalent iron salt and pH adjusting agent are added in the aqueous solution of tween/ethylene glycol, are uniformly mixed, obtain forerunner
Liquid solution；
(b) precursor solution is placed in hydro-thermal reaction 8-15h at 150-200 DEG C, obtains sediment；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electricity with hollow rod structure
Pole material Fe2O3。
Further, the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:(4-15):(20-
50), preferably 1:(4-12):(22-40), further preferably 1:(4-10):(25-30).
Further, in step (a), the mass ratio of trivalent iron salt and pH adjusting agent is (400-600):1, preferably
(440-560):1, further preferably (480-520):1；
Preferably, the trivalent iron salt include in ferric chloride hexahydrate, ferric nitrate or ferric sulfate any one or extremely
Few two kinds of combination；
Preferably, the pH adjusting agent is dihydric phosphate, further preferably sodium dihydrogen phosphate and/or biphosphate
Potassium, more preferably sodium dihydrogen phosphate.
Further, in step (a), the pH of the precursor solution is 9-11, preferably 9-10.
Further, in step (b), the temperature of hydro-thermal reaction is 160-190 DEG C, preferably 170-185 DEG C, further excellent
It is selected as 175-180 DEG C；
And/or the time of hydro-thermal reaction is 9-14h, preferably 10-13h, further preferably 11-12h.
Further, in step (c), sediment absolute ethyl alcohol and deionized water are washed and is centrifuged respectively is several
It is secondary；
Preferably, sediment absolute ethyl alcohol and deionized water are washed respectively and centrifuged three times.
Further, in step (c), drying temperature is 60-90 DEG C, preferably 65-85 DEG C, further preferably 70-80
℃；
And/or drying time 20-30h, preferably 22-28h, further preferably 24-26h.
Further, the battery electrode material Fe2O3Preparation method, include the following steps：
(a) ferric chloride hexahydrate, ferric sulfate and sodium dihydrogen phosphate are added in the aqueous solution of tween/ethylene glycol, are mixed
Uniformly, precursor solution is obtained, wherein the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:(4-
15):(20-50)；
(b) hydro-thermal reaction 8-15h at a temperature of precursor solution being placed in 150-200 DEG C；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electricity with hollow rod structure
Pole material Fe2O3；
Preferably, the battery electrode material Fe2O3Preparation method, include the following steps：
(a) ferric chloride hexahydrate, ferric sulfate and sodium dihydrogen phosphate are added in the aqueous solution of tween/ethylene glycol, are mixed
Uniformly, precursor solution is obtained, wherein the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:10:
25；
(b) precursor solution is placed in hydro-thermal reaction 12h at 180 DEG C；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electricity with hollow rod structure
Pole material Fe2O3。
The present invention also provides a kind of battery electrode material Fe2O3, using above-mentioned battery electrode material Fe2O3Preparation
Method is prepared, the battery electrode material Fe2O3With hollow rod structure.
The present invention also provides a kind of lithium ion batteries, including above-mentioned battery electrode material Fe2O3。
Compared with prior art, battery electrode material Fe provided by the invention2O3Preparation method and application have and following have
Beneficial effect：
(1) the present invention provides a kind of battery electrode material Fe2O3Preparation method spat mainly using trivalent iron salt as source of iron
The aqueous solution of temperature/ethylene glycol is prepared by hydro-thermal method with hollow as guiding growth agent using pH adjusting agent adjusting ambient pH
The battery electrode material Fe of rod structure2O3Nano material, wherein the aqueous solution of guiding growth agent tween/ethylene glycol is not only able to adjust
The boiling point of hydro-thermal reaction is controlled, and tween forms colloid in aqueous solution, generate absorption electric double layer, absorption iron ion is oriented to life
It is long, so that Fe2O3Pattern be easier to control, and Fe2O3Hollow rod structure can not only provide bigger reaction contact
Area, and make Fe2O3Electric conductivity it is more preferable, be conducive to provide the ion transmission channel of bigger, enhance cyclical stability, into
And improve the chemical property of material.
(2) battery electrode material Fe provided by the invention2O3Preparation method, have it is simple for process, synthesis temperature is low, protect
The advantages that warm time is short, the ingredient of synthesis is uniform, crystal morphology is good, object phase purity is high.
(3) the present invention also provides battery electrode material Fe2O3, it is made using above-mentioned preparation method, the battery electrode material
Fe2O3With hollow rod structure, which can make Fe2O3Specific surface area reach maximization, preferably utilize its space,
The stability of material structure is kept, enhances cyclical stability, and then ensure the excellent chemical property of material, improves existing
Fe2O3The technical problem that poorly conductive, cyclical stability be not good enough.
(4) the present invention also provides a kind of lithium ion batteries, including above-mentioned battery electrode material Fe2O3.In view of above-mentioned battery
Electrode material Fe2O3Possessed advantage so that there is higher specific volume using its lithium ion battery as cell negative electrode material
The chemical properties such as amount, good electric conductivity and cyclical stability.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the battery electrode material Fe obtained by embodiment 12O3X-ray diffractogram；
Fig. 2 is the battery electrode material Fe obtained by embodiment 12O3Scanning electron microscope (SEM) photograph；
Fig. 3 is using the battery electrode material Fe obtained by embodiment 12O3Half-cell obtained is the 0.1A/g under the conditions of
Charging and discharging curve.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of battery electrode material Fe is provided2O3Preparation method, including it is as follows
Step；
(a) trivalent iron salt and pH adjusting agent are added in the aqueous solution of tween/ethylene glycol, are uniformly mixed, obtain forerunner
Liquid solution；
(b) precursor solution is placed in hydro-thermal reaction 8-15h at 150-200 DEG C, obtains sediment；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electricity with hollow rod structure
Pole material Fe2O3。
Hydro-thermal method refer in special closed reactor (autoclave), using aqueous solution as reaction system, pass through by
Reaction system is heated to critical-temperature (or close to critical-temperature), generates hyperbaric environment in the reaction system and carries out Inorganic synthese
With a kind of method of material preparation.The present invention prepares battery electrode material Fe using hydro-thermal method2O3, hydro-thermal method generally be not necessarily to sintering,
This can to avoid in sintering process crystal grain grow up, to obtain, crystal form is good and controllable Fe2O3Material, and production cost
It is low.
Specifically, trivalent iron salt is used as bulk in the present invention, primarily to providing source of iron, utilization is ferric
Oxidisability.Using the trivalent iron salt that this field is common, such as ferric chloride hexahydrate, ferric nitrate, ferric sulfate, do not make spy herein
It is different to limit.
"/" in the aqueous solution of tween/ethylene glycol represent " and " the meaning, the aqueous solution of tween/ethylene glycol refers to tween
With the aqueous solution of ethylene glycol, i.e., water-miscible organic solvent tween and ethylene glycol are added into water.Xiang Shuizhong adds tween and second two
On the one hand alcohol can utilize the boiling point of tween and ethylene glycol regulation and control aqueous solution, on the other hand utilize organic solvent tween and second two
The guiding growth of alcohol acts on, i.e., tween forms colloid in aqueous solution, generates absorption electric double layer, adsorbs iron ion guiding growth,
I.e. the aqueous solution of tween/ethylene glycol is used as structure directing agent in the present invention, to control Fe2O3The pattern and crystal form of crystal.
Battery electrode material Fe provided by the invention2O3Preparation method, mainly using trivalent iron salt as source of iron, tween/second two
The aqueous solution of alcohol is prepared by hydro-thermal method with hollow rod structure as guiding growth agent, pH adjusting agent adjusting ambient pH
Battery electrode material Fe2O3, wherein by the regulation and control of the aqueous solution to guiding growth agent tween/ethylene glycol, and combine hydro-thermal
The advantages of method, it will be able to prepare the Fe with hollow rod structure2O3Nano material is realized to Fe2O3Granule-morphology fine structure
Control.Obtained Fe2O3This specific hollow rod structure the reaction contact area of bigger, Er Qiezhong can be not only provided
The Fe of void column structure2O3Electric conductivity it is more preferable, be conducive to provide the ion transmission channel of bigger, and then improve the electrochemistry of material
Performance.
As a kind of preferred embodiment of the present invention, the body of tween, ethylene glycol and water in the aqueous solution of tween/ethylene glycol
Product is than being 1:(4-15):(20-50), preferably 1:(4-12):(22-40), further preferably 1:(4-10):(25-30), more
Preferably 1:10:25.
The consumption proportion of tween, ethylene glycol and water has the performance of guiding growth agent in the aqueous solution of tween/ethylene glycol
It directly affects, the dosage of tween and ethylene glycol is excessive or very few is unfavorable for for Fe2O3The regulation and control of pattern.
The volume ratio of typical but non-limiting tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:4:20、
1:4:30、1:4:40、1:4:50、1:5:20、1:5:30、1:5:40、1:5:50、1:8:20、1:8:30、1:8:40、1:8:50、
1:10:20、1:10:30、1:10:40、1:10:50、1:12:20、1:12:30、1:12:40、1:12:50、1:15:20、1:15:
30、1:15:40 or 1:15:50.
As a kind of preferred embodiment of the present invention, in step (a), the mass ratio of trivalent iron salt and pH adjusting agent is
(400-600):1, preferably (440-560):1, further preferably (480-520):1；
Proportioning between trivalent iron salt and pH adjusting agent should also control in suitable numberical range.It is typical but unrestricted
Property trivalent iron salt and pH adjusting agent mass ratio be 400:1、420:1、450:1、460:1、480:1、500:1、510:1、
520:1、530:1、540:1、550:1、560:1、570:1、580:1、590:1、600:1。
As a kind of preferred embodiment of the present invention, the trivalent iron salt includes ferric chloride hexahydrate, ferric nitrate or sulphur
In sour iron any one or at least two combination.
In order to obtain the Fe of higher degree2O3, further preferably ferric chloride hexahydrate and/or ferric sulfate is as source of iron.
As a kind of preferred embodiment of the present invention, the pH adjusting agent is dihydric phosphate, further preferably phosphorus
Acid dihydride sodium and/or potassium dihydrogen phosphate, more preferably sodium dihydrogen phosphate.
As a kind of preferred embodiment of the present invention, in step (a), the pH of the precursor solution is 9-11, preferably
For 9-10.
By the addition of pH adjusting agent, the pH of precursor solution is adjusted, typical but non-limiting pH is 9,10 or 11.
As a kind of preferred embodiment of the present invention, in step (b), the temperature of hydro-thermal reaction is 160-190 DEG C, preferably
It is 170-185 DEG C, further preferably 175-180 DEG C；
And/or the time of hydro-thermal reaction is 9-14h, preferably 10-13h, further preferably 11-12h.
Typical but non-limiting temperature is 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C or 190 DEG C；Hydro-thermal
It is 9h, 10h, 11h, 12h, 13h or 14h to react the typical but non-limiting time.
The temperature of hydro-thermal reaction can influence the species activity in reaction process, influence the type for generating substance, while also shadow
Ring the generation quality and the speed of growth of crystal, and the time of hydro-thermal reaction can then influence the crystal of growth crystalline structure and
Crystallite dimension.By the restriction of the temperature and time to above-mentioned hydro-thermal reaction, make that the higher Fe of quality is obtained by the reaction2O3。
It should be noted that various influence factors mutually restrict in hydrothermal reaction process.Therefore to prepare pattern, crystalline substance
The good crystal of type needs to consider the factor for being possible to influence crystal growth.
As a kind of preferred embodiment of the present invention, in step (c), by sediment absolute ethyl alcohol and deionization moisture
It is not washed and is centrifuged several times；
Preferably, sediment absolute ethyl alcohol and deionized water are washed respectively and centrifuged three times.
Sediment repeatedly wash and centrifuge, the impurity in sediment can be effectively removed, improve the pure of sediment
Degree.
As a kind of preferred embodiment of the present invention, in step (c), drying temperature is 60-90 DEG C, preferably 65-85
DEG C, further preferably 70-80 DEG C；
And/or drying time 20-30h, preferably 22-28h, further preferably 24-26h.
Typical but non-limiting drying temperature is 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；It is typical but
Unrestricted drying time be 20h, 22h, for 24 hours, 26h, 28h or 30h.
Pass through the restriction to drying temperature and time so that obtained Fe2O3Reach good drying effect.
As a kind of preferred embodiment of the present invention, the battery electrode material Fe2O3Preparation method, including it is as follows
Step：
(a) ferric chloride hexahydrate, ferric sulfate and sodium dihydrogen phosphate are added in the aqueous solution of tween/ethylene glycol, are mixed
Uniformly, precursor solution is obtained, wherein the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:(4-
15):(20-50)；
(b) hydro-thermal reaction 8-15h at a temperature of precursor solution being placed in 150-200 DEG C；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electricity with hollow rod structure
Pole material Fe2O3。
Preferably, the battery electrode material Fe2O3Preparation method, include the following steps：
(a) ferric chloride hexahydrate, ferric sulfate and sodium dihydrogen phosphate are added in the aqueous solution of tween/ethylene glycol, are mixed
Uniformly, precursor solution is obtained, wherein the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:10:
25；
(b) precursor solution is placed in hydro-thermal reaction 12h at 180 DEG C；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electricity with hollow rod structure
Pole material Fe2O3。
Use Iron(III) chloride hexahydrate and ferric sulfate for source of iron in the present invention, sodium dihydrogen phosphate provides acidic environment, spits
The aqueous solution of temperature/ethylene glycol is as guiding growth agent, and by battery electrode material Fe2O3The specific restriction of preparation method, makes
Obtain the prepared battery electrode material Fe with hollow rod structure out2O3Has good crystal morphology.
Above-mentioned preparation method is with simple for process, synthesis temperature is low, soaking time is short, the ingredient of synthesis is uniform, crystal shape
The advantages that looks are good, object phase purity is high.
According to the second aspect of the invention, a kind of battery electrode material Fe is additionally provided2O3, using above-mentioned battery electricity
Pole material Fe2O3Preparation method be prepared, the battery electrode material Fe2O3With hollow rod structure.
Above-mentioned specific structure can make battery electrode material Fe2O3Specific surface area reach maximization, preferably utilize its empty
Between, the stability of material structure is kept, enhances cyclical stability, and then ensure the excellent chemical property of material.
According to the third aspect of the present invention, a kind of lithium ion battery, including above-mentioned battery electrode material are additionally provided
Fe2O3。
In view of above-mentioned battery electrode material Fe2O3Possessed advantage so that using its as cell negative electrode material lithium from
Sub- battery has higher specific capacity and the chemical properties such as good electric conductivity and cyclical stability.
With reference to specific embodiment and comparative example, the invention will be further described.It should be noted that following implement
Drug used is purchased from Sinopharm Chemical Reagent Co., Ltd. in example and comparative example.
Embodiment 1
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, include the following steps：
(a) tween and ethylene glycol is soluble in water, stir to get the aqueous solution of tween/ethylene glycol, tween, ethylene glycol and water
Volume ratio be 1:4:20；
0.6488g ferric chloride hexahydrates, 0.6488g ferric sulfate and 0.0025g sodium dihydrogen phosphates are added to tween/second two
In the aqueous solution of alcohol, container bottom is stirred well to without precipitation, obtains precursor solution；
(b) precursor solution is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, hydro-thermal at a temperature of being placed in 180 DEG C
12h is reacted, sediment is obtained；
(c) step (b) sediment obtained by the reaction is washed and is centrifuged respectively three times using absolute ethyl alcohol and deionized water,
The solid obtained after centrifugation is dry at 80 DEG C, obtain the battery electrode material Fe with hollow rod structure2O3。
Embodiment 2
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition in step (a) use 1.2975g
Ferric chloride hexahydrate, 1.2975g ferric sulfate and 0.005g sodium dihydrogen phosphates, remaining step and technological parameter and 1 phase of embodiment
Together.
Embodiment 3
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition in step (a) use 1.9464g
Ferric chloride hexahydrate, 1.9464g ferric sulfate and 0.0075g sodium dihydrogen phosphates, remaining step and technological parameter and 1 phase of embodiment
Together.
Embodiment 4
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition in step (a) use 0.6488g
Ferric chloride hexahydrate, 1.2975g ferric sulfate and 0.0048g sodium dihydrogen phosphates, remaining step and technological parameter and 1 phase of embodiment
Together.
Embodiment 5
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition in step (a) use 0.6488g
Ferric chloride hexahydrate, 1.2975g ferric sulfate and 0.0034g sodium dihydrogen phosphates, remaining step and technological parameter and 1 phase of embodiment
Together.
Embodiment 6
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition to step (a) tween/ethylene glycol
The volume ratio of tween, ethylene glycol and water is 1 in aqueous solution:10:25, remaining step and technological parameter are same as Example 1.
Embodiment 7
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition to step (a) tween/ethylene glycol
The volume ratio of tween, ethylene glycol and water is 1 in aqueous solution:15:50, remaining step and technological parameter are same as Example 1.
Embodiment 8
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition to step (a) tween/ethylene glycol
The volume ratio of tween, ethylene glycol and water is 1 in aqueous solution:3:20, remaining step and technological parameter are same as Example 1.
Embodiment 9
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, in addition to step (a) tween/ethylene glycol
The volume ratio of tween, ethylene glycol and water is 1 in aqueous solution:20:20, remaining step and technological parameter are same as Example 1.
Embodiment 10
A kind of battery electrode material Fe provided in this embodiment2O3Preparation method, include the following steps：
(a) tween and ethylene glycol is soluble in water, stir to get the aqueous solution of tween/ethylene glycol, tween, ethylene glycol and water
Volume ratio be 1:8:30；
0.6488g ferric nitrates, 0.6488g ferric sulfate and 0.0025g sodium dihydrogen phosphates are added to the water of tween/ethylene glycol
In solution, container bottom is stirred well to without precipitation, obtains precursor solution；
(b) precursor solution is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, hydro-thermal at a temperature of being placed in 160 DEG C
14h is reacted, sediment is obtained；
(c) step (b) sediment obtained by the reaction is washed and is centrifuged respectively three times using absolute ethyl alcohol and deionized water,
The solid obtained after centrifugation is dry at 90 DEG C, obtain the battery electrode material Fe with hollow rod structure2O3。
Comparative example 1
A kind of battery electrode material Fe that this comparative example provides2O3Preparation method, in addition to by tween/second in step (a)
The aqueous solution of glycol replaces with water, remaining step and technological parameter are same as Example 1.
Comparative example 2
A kind of battery electrode material Fe that this comparative example provides2O3Preparation method, in addition to by tween/second in step (a)
The aqueous solution of glycol replaces with the aqueous solution of tween, remaining step and technological parameter are same as Example 1.
Comparative example 3
A kind of battery electrode material Fe that this comparative example provides2O3Preparation method, in addition to by tween/second in step (a)
The aqueous solution of glycol replaces with the aqueous solution of ethylene glycol, remaining step and technological parameter are same as Example 1.
Comparative example 4
A kind of battery electrode material Fe that this comparative example provides2O3Preparation method, in addition to hydro-thermal reaction in step (b)
Temperature is other than 140 DEG C, remaining step and technological parameter are same as Example 1.
Further to verify the effect of embodiment and comparative example, ad hoc following experimental example.
Experimental example 1
(1) battery electrode material Fe obtained to each embodiment and comparative example2O3X-ray diffraction is carried out, herein only with reality
It applies and illustrates for example 1, be specifically shown in Fig. 1.
Can be seen that by XRD spectrum, characteristic peak respectively 2 θ=33.82 °, 2 θ=35.40 °, 2 θ=49.01 °, 2 θ=
54.80 °, the positions such as 2 θ=58.24 ° and 2 θ=65.99 °, by standard of comparison spectrogram (JCPDS Card No.33-0664),
Above-mentioned diffraction maximum is respectively α-Fe2O3(104), (110), (024), (116), (122) and (125) crystal face.
(2) battery electrode material Fe obtained to each embodiment and comparative example2O3Electron-microscope scanning is carried out, herein only with reality
It applies and illustrates for example 1, be specifically shown in Fig. 2.
By Fig. 2, it is apparent that battery electrode material Fe2O3Pattern be hollow rod structure, and size is more uniform.
(3) respectively by battery electrode material Fe made from embodiment 1-10 and comparative example 1-42O3Half-cell is made, half electricity
Pond assembly method is as follows：
By the mesuring battary electrode material Fe of preparation2O3, Super P Li conductive blacks and PVDF be 85 in mass ratio:10:
5 mixing, are mixed well with N-Methyl pyrrolidone and stir into thick, be then coated on copper foil, vacuum at 60 DEG C (-
It is 0.1MPa) 6 hours dry, the circular film of diameter about 1cm is cut into after cooling.Half-cell is buckled in glove box using CR2016 types
Formula battery assemble, diaphragm be 2400 polypropylene diaphragms of Celgard, electrolyte be the LiPF6 containing 1M ethylene carbonate (EC) with
(volume ratio of EC, DEC are 1 to diethyl carbonate (DEC) mixed electrolytic solution in mixed electrolytic solution:1), cathode is the round lithium of commercialization
Piece (diameter 1.5cm).
Using blue electricity CT2001A types battery test system (Wuhan Land Electronic Co., Ltd.'s production) to embodiment
Battery electrode material Fe made from 1-10 and comparative example 1-42O3Manufactured half-cell carries out electrochemical property test, specific to tie
Fruit is shown in Table 1.Wherein, charging and discharging curve carries out under the conditions of 0.1A/g.
Chemical property of the table 1 using each embodiment and comparative example as lithium ion battery made from negative material
As can be seen from Table 1, the battery electrode material Fe provided using embodiment 1-102O3Lithium ion battery obtained
Chemical property will integrally be better than the battery electrode material Fe provided using comparative example 1-42O3Lithium ion battery obtained.
Specifically, embodiment 4 and 5 is the control experiment of embodiment 1, three is the difference is that trivalent iron salt is adjusted with pH
The mass ratio of agent is different.Trivalent iron salt and the mass ratio of pH adjusting agent are by influencing battery electrode it can be seen from data in table 1
Material Fe2O3And then the chemical property of lithium ion battery is had an impact.
Embodiment 6-9 is the control experiment of embodiment 1.Several persons in the aqueous solution of tween/ethylene glycol the difference is that spit
Temperature, ethylene glycol are different with the volume ratio of water.The volume ratio of tween, ethylene glycol and water passes through influence it can be seen from data in table 1
Battery electrode material Fe2O3Crystal morphology so that influence lithium ion battery chemical property.Only when guiding growth agent is spat
The volume ratio of tween, ethylene glycol and water is in the numberical range that the present invention limits in the aqueous solution of temperature/ethylene glycol, battery electrode material
Expect Fe2O3Specific hollow rod structure could be formed, the reaction contact area of bigger can be not only provided, improves electric conductivity, also
Cyclical stability can be enhanced, as the negative material of lithium ion battery, the chemical property of lithium ion battery may make to obtain
It is promoted to further.
Wherein, Fig. 3 is 1 corresponding charging and discharging curve of embodiment.As seen from Figure 3, battery electrode material Fe2O3Head
Secondary specific discharge capacity can reach 1050.1mAh/g, and initial charge specific capacity can reach 1039.9mAh/g, closely
Fe2O3Theoretical charging and discharging capacity (1005mAh/g).Under the multiplying power of 1C, material specific capacity does not decline substantially in cyclic process
Subtract, the specific discharge capacity of material is 863.5mAh/g after 100 cycles, and specific discharge capacity conservation rate is 83.1%.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of battery electrode material iron oxide, which is characterized in that include the following steps：
(a) trivalent iron salt and pH adjusting agent are added in the aqueous solution of tween/ethylene glycol, are uniformly mixed, it is molten obtains presoma
Liquid；
(b) precursor solution is placed in hydro-thermal reaction 8-15h at 150-200 DEG C, obtains sediment；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electrode material with hollow rod structure
Expect iron oxide.
2. the preparation method of battery electrode material iron oxide according to claim 1, which is characterized in that tween/ethylene glycol
Aqueous solution in tween, ethylene glycol and water volume ratio be 1:(4-15):(20-50), preferably 1:(4-12):(22-40), into
One step is preferably 1:(4-10):(25-30).
3. the preparation method of battery electrode material iron oxide according to claim 1, which is characterized in that in step (a), three
Valence molysite and the mass ratio of pH adjusting agent are (400-600):1, preferably (440-560):1, further preferably (480-
520):1；
Preferably, the trivalent iron salt includes any one in ferric chloride hexahydrate, ferric nitrate or ferric sulfate or at least two
The combination of kind；
Preferably, the pH adjusting agent is dihydric phosphate, further preferably sodium dihydrogen phosphate and/or potassium dihydrogen phosphate, more
Preferably sodium dihydrogen phosphate.
4. the preparation method of battery electrode material iron oxide according to claim 1, which is characterized in that in step (a), institute
The pH for stating precursor solution is 9-11, preferably 9-10.
5. the preparation method of battery electrode material iron oxide according to any one of claims 1-4, which is characterized in that step
Suddenly in (b), the temperature of hydro-thermal reaction is 160-190 DEG C, preferably 170-185 DEG C, further preferably 175-180 DEG C；
And/or the time of hydro-thermal reaction is 9-14h, preferably 10-13h, further preferably 11-12h.
6. the preparation method of battery electrode material iron oxide according to any one of claims 1-4, which is characterized in that step
Suddenly in (c), sediment absolute ethyl alcohol and deionized water is washed respectively and centrifuged several times；
Preferably, sediment absolute ethyl alcohol and deionized water are washed respectively and centrifuged three times.
7. the preparation method of battery electrode material iron oxide according to any one of claims 1-4, which is characterized in that step
Suddenly in (c), drying temperature is 60-90 DEG C, preferably 65-85 DEG C, further preferably 70-80 DEG C；
And/or drying time 20-30h, preferably 22-28h, further preferably 24-26h.
8. the preparation method of battery electrode material iron oxide according to any one of claims 1-4, which is characterized in that packet
Include following steps：
(a) ferric chloride hexahydrate, ferric sulfate and sodium dihydrogen phosphate are added in the aqueous solution of tween/ethylene glycol, are uniformly mixed,
Obtain precursor solution, wherein the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:(4-15):
(20-50)；
(b) hydro-thermal reaction 8-15h at a temperature of precursor solution being placed in 150-200 DEG C；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electrode material with hollow rod structure
Expect iron oxide；
Preferably, the preparation method of the battery electrode material iron oxide, includes the following steps：
(a) ferric chloride hexahydrate, ferric sulfate and sodium dihydrogen phosphate are added in the aqueous solution of tween/ethylene glycol, are uniformly mixed,
Obtain precursor solution, wherein the volume ratio of tween, ethylene glycol and water is 1 in the aqueous solution of tween/ethylene glycol:10:25；
(b) precursor solution is placed in hydro-thermal reaction 12h at 180 DEG C；
(c) step (b) sediment obtained by the reaction is washed, is centrifuged, it is dry, obtain the battery electrode material with hollow rod structure
Expect iron oxide.
9. a kind of battery electrode material iron oxide, which is characterized in that using the battery electrode described in claim 1-8 any one
The preparation method of material oxidation iron is made, and the battery electrode material iron oxide has hollow rod structure.
10. a kind of lithium ion battery, which is characterized in that including the battery electrode material iron oxide described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810333107.6A CN108428887B (en) | 2018-04-13 | 2018-04-13 | Preparation method of battery electrode material ferric oxide, battery electrode material ferric oxide and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810333107.6A CN108428887B (en) | 2018-04-13 | 2018-04-13 | Preparation method of battery electrode material ferric oxide, battery electrode material ferric oxide and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108428887A true CN108428887A (en) | 2018-08-21 |
| CN108428887B CN108428887B (en) | 2020-07-31 |
Family
ID=63161021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810333107.6A Active CN108428887B (en) | 2018-04-13 | 2018-04-13 | Preparation method of battery electrode material ferric oxide, battery electrode material ferric oxide and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108428887B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333103A (en) * | 2008-07-30 | 2008-12-31 | 江苏工业学院 | Method for synthesizing ferrimagnetism hollow microballoons |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN103066280A (en) * | 2012-12-28 | 2013-04-24 | 珠海泰坦能源电子技术有限公司 | Spherical lithium iron phosphate anode material and preparation method thereof |
| CN103754956A (en) * | 2013-12-31 | 2014-04-30 | 太原理工大学 | Hydro-thermal synthesis method for shape-controllable nano iron oxide |
| CN104003448A (en) * | 2014-05-20 | 2014-08-27 | 江苏大学 | [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof |
| CN104815658A (en) * | 2015-04-09 | 2015-08-05 | 太原理工大学 | Tetrahexahedron iron oxide nanocrystalline catalyst, preparation method and application thereof |
-
2018
- 2018-04-13 CN CN201810333107.6A patent/CN108428887B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333103A (en) * | 2008-07-30 | 2008-12-31 | 江苏工业学院 | Method for synthesizing ferrimagnetism hollow microballoons |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN103066280A (en) * | 2012-12-28 | 2013-04-24 | 珠海泰坦能源电子技术有限公司 | Spherical lithium iron phosphate anode material and preparation method thereof |
| CN103754956A (en) * | 2013-12-31 | 2014-04-30 | 太原理工大学 | Hydro-thermal synthesis method for shape-controllable nano iron oxide |
| CN104003448A (en) * | 2014-05-20 | 2014-08-27 | 江苏大学 | [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof |
| CN104815658A (en) * | 2015-04-09 | 2015-08-05 | 太原理工大学 | Tetrahexahedron iron oxide nanocrystalline catalyst, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王晓倩等: "形貌可控的氧化铁中空柱的制备", 《无极化学学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108428887B (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101335348B (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 | |
| CN101693532B (en) | Method for preparing lithium ferrous phosphate | |
| CN108075111A (en) | Lithium ion battery and positive electrode material thereof | |
| CN111430677B (en) | Negative electrode material and preparation method thereof, negative electrode and lithium ion battery | |
| CN108899531A (en) | A kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material | |
| CN105977465A (en) | Method for preparing graphene/lithium iron phosphate composite anode materials | |
| CN108017050A (en) | A kind of doped graphene and its preparation method and application | |
| CN109950530A (en) | With the nickelic tertiary cathode material and preparation method thereof for improving electrical property | |
| CN106571452A (en) | Lithium ion battery positive electrode material and preparation method thereof | |
| JP6182673B2 (en) | Method for producing lithium iron phosphate | |
| CN107887583A (en) | A kind of doped lithium iron phosphate anode material and preparation method thereof | |
| CN108565432A (en) | LiFePO4/nitrogen, sulphur codope graphene composite material and preparation method thereof | |
| CN101081695A (en) | Preparation method of doped modified ferric phosphate lithium | |
| CN106784659A (en) | Spinel layered heterostructure material and preparation method thereof | |
| CN110156080B (en) | Growth V of carbon cloth5.45S8Preparation method and application of single crystal nanosheet | |
| CN103159201B (en) | A kind of high pressure, low temperature method preparing carbon-coated LiFePO 4 for lithium ion batteries anode composite material of lithium ion battery | |
| CN105810910B (en) | A kind of Na2‑2xFe1+xP2O7/ carbon composite and its preparation method and application | |
| CN110120503B (en) | Composite cathode material and preparation method and application thereof | |
| CN106450186A (en) | Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application | |
| CN106684382A (en) | Preparation method of lithium iron phosphate/graphene composite material | |
| CN106058221B (en) | A kind of preparation method of the compound manganese salt cladding lithium-rich manganese-based anode material of phosphate radical polyanion | |
| CN107195884B (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| CN108767231A (en) | A kind of LiNixCoyMnl-x-yO2/Li2O·B2O3The preparation method of composite positive pole | |
| CN102983332A (en) | Preparation method for lithium iron phosphate material of positive electrode of lithium ion secondary battery | |
| CN107123802A (en) | A kind of preparation method of graphene modified phosphate iron lithium material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |