CN102637869A - A kind of Fe2O3 nano rod and its preparation method and application - Google Patents
A kind of Fe2O3 nano rod and its preparation method and application Download PDFInfo
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Abstract
一种Fe2O3纳米棒及其制备方法和用途，属于纳米材料技术领域。解决现有Fe2O3纳米棒合成方法制备过程繁琐和对温度要求苛刻的问题。该Fe2O3纳米棒将二价铁化合物和草酸盐化合物混合，经洗涤、烘干、研磨后，形成粉末，化合物粉末在空气中以1-10℃/min升温速率加热，300-700℃条件下煅烧0.5-5h，以1-10℃/min降温速率冷却至室温而得到的。该方法工艺简单，反应物混合均匀，制得的Fe2O3纳米棒平均粒径为30纳米，平均长度可达2微米。由该Fe2O3纳米棒作为锂离子二次电池负极材料在首次放电容量可达1265mAh/g，库伦效率为71.23％，四次循环后其库伦效率达到93.72％。
An Fe 2 O 3 nanorod and its preparation method and application belong to the technical field of nanomaterials. The method solves the problems of cumbersome preparation process and strict requirement on temperature in the existing synthesis method of Fe 2 O 3 nanorods. The Fe 2 O 3 nanorods are mixed with a ferrous compound and an oxalate compound, washed, dried, and ground to form a powder, and the compound powder is heated in the air at a heating rate of 1-10°C/min, 300-700 It is obtained by calcining at ℃ for 0.5-5h and cooling to room temperature at a cooling rate of 1-10℃/min. The method has simple process, uniform mixing of reactants, and the prepared Fe 2 O 3 nanorods have an average particle diameter of 30 nanometers and an average length of up to 2 micrometers. The Fe 2 O 3 nanorod is used as the negative electrode material of the lithium ion secondary battery, the first discharge capacity can reach 1265mAh/g, the coulombic efficiency is 71.23%, and the coulombic efficiency reaches 93.72% after four cycles.
Description
Technical field
The invention belongs to nano material and lithium battery applications technical field, be specifically related to a kind of Fe
2O
3Nanometer rods.
Background technology
Ferrous oxalate, English Ferrous oxalate by name, the CAS accession number is 6047-25-2, molecular formula is FeC
2O
42H
2O; Di-iron trioxide has another name called iron oxide, English Ferric odide by name, and the CAS accession number is 1309-37-1, molecular formula is Fe
2O
3Ferrous oxalate and di-iron trioxide be important chemical material be again important product.
Current social development along with electronic product, small sized product such as mobile phone, digital camera, laptop computer etc., large product such as electric bicycle, electric automobile etc. have all got in people's the life.Battery receives the concern in the whole world as the important formation of electric energy and storage mode.Have extended cycle life, the charge-discharge performance of environmental friendliness, height ratio capacity, the lithium rechargeable battery of high enclosed pasture efficient become the outstanding person in the battery; In batteries such as lead accumulator and Ni-MH battery, show one's talent, be considered to the most rising energy storage and power accumulator material.
Since the lithium ion battery commercialization; The negative material of research mainly contains material with carbon element (graphite, disordered carbon), carbon compound (B-C-N based compound, C-Si-O based compound), non-material with carbon element (metal oxide, lithium-transition metal nitride, lithium alloy); And be widely used in some small-sized electronic products; But in this large-scale electronic product of electric motor car field, still can't meet the demands.
Should meet following requirement at the industrial carbon negative electrode material of lithium ion cell that is applied;
1. Gibbs free is little in the insertion reaction of lithium ion;
2. lithium ion has high diffusivity in the solid-state structure of negative pole;
3. highly reversible insertion reaction;
4. good conductivity is arranged;
5. the stable while does not react with electrolyte on the thermodynamics.
At present, what use in the commercialization lithium ion battery mainly is graphited material with carbon element and a spot of non-graphitized hard carbon material, and other negative material still is in conceptual phase, does not form sizable application.Therefore, study high performance negative material, the performance that improves power lithium-ion battery is the research direction of a key.Fe wherein
2O
3Have good cycle performance and quite high specific capacity (1005mAh/g) as the metal oxide negative material.
Nano material is because yardstick is little, and the characteristics that specific area is big as lithium ion battery electrode material, show some superiority:
1. can improve Li
+The dynamic performance of storage;
2. improve the structural stability of material;
3. form new storage lithium mechanism;
Traditional Fe
2O
3The nanometer rods synthetic method has methods such as direct template method, sol-gel process, coprecipitation and hydrothermal/solvent heat; But these methods or preparation process are loaded down with trivial details; Or only suitable laboratory prepares on a small quantity; That have even very harsh to conditional requests such as temperature, these all largely limit its commercialization as lithium ion battery negative material.
Summary of the invention
The objective of the invention is in order to solve existing Fe
2O
3The nanometer rods synthetic method prepare process loaded down with trivial details, can not prepare in a large number and the problem harsh temperature requirement, and a kind of Fe is provided
2O
3Nanometer rods.With the synthetic Fe of this method
2O
3The nanometer rods even particle distribution, technology is simple.
The present invention provides a kind of Fe
2O
3The preparation method of nanometer rods comprises the steps:
Step 1: ferro-compound and oxalates compound are dissolved in respectively in the solvent, again both mixing are obtained product, the mol ratio of described ferro-compound and oxalates compound is 1: 1～2;
Step 2: product suction filtration, washing, oven dry, grinding with step 1 obtains obtain compound powder;
Step 3: the compound powder that step 2 is obtained heats with 1-10 ℃/min heating rate in air, calcines 0.5-5h under the 300-700 ℃ of condition, is cooled to room temperature with 1-10 ℃/min rate of temperature fall, promptly obtains Fe
2O
3Nanometer rods.
Preferably, said ferro-compound is selected from one or both in frerrous chloride or the ferrous acetate, more preferably frerrous chloride.
Preferably, said oxalates compound is selected from one or more in oxalic acid, potassium oxalate or the ammonium oxalate, more preferably oxalic acid.
Preferably, said solvent is selected from one or more in absolute ethyl alcohol, methyl alcohol, industrial alcohol or the water, more preferably absolute ethyl alcohol.
The present invention also provides according to above-mentioned a kind of Fe
2O
3The Fe of preparation method's preparation of nanometer rods
2O
3Nanometer rods.
The present invention also provides above-mentioned Fe
2O
3The application of nanometer rods in the preparation lithium ion battery.
Beneficial effect of the present invention
1, a kind of Fe of the present invention
2O
3The preparation method of nanometer rods adopts absolute ethyl alcohol to make solvent, makes ferro-compound generate the ferrous oxalate compound with the oxalates compound at once once contacting; Crystallization rate makes ferrous oxalate ramp in one direction soon, generates very narrow nano strip compound, and this method technology is simple; Be suitable for large-scale production; Low in raw material cost need not consume a large amount of alcoholic solvents, and reactant mixes; The ferrous oxalate of nano strip and airborne oxygen contact area are bigger, make that the ferrous oxalate oxidation is more complete.
2, by the Fe that a process for preparing
2O
3Nanometer rods has homogeneous phase, high, the evengranular advantage of degree of crystallinity, the Fe of generation
2O
3The nanometer rods particle diameter is the 30-70 nanometer, and length can reach the 0.2-4 micron.
3, by Fe of the present invention
2O
3The lithium ion battery negative material of nanometer rods preparation has good electrochemical, because Fe
2O
3Nanometer rods is complete with the electrolyte full contact in electrochemical reaction, can improve the charge/discharge capacity under the high magnification condition, has higher capacity, better cycle ability and high rate performance, and experimental result shows: Fe
2O
3Nanometer rods can reach 1265mAh/g as ion secondary battery cathode material lithium in discharge capacity first, and enclosed pasture efficient is that 71.23%, four circulation back its coulomb efficient reaches 93.72%, and remains unchanged basically.
Description of drawings
Fig. 1 is the ferrous oxalate and the Fe of the embodiment of the invention 1 preparation
2O
3The ESEM picture of nanometer rods;
Fig. 2 is the Fe of the embodiment of the invention 1 preparation
2O
3The transmission electron microscope picture of nanometer rods;
Fig. 3 is the ferrous oxalate and the Fe of the embodiment of the invention 1 preparation
2O
3The XRD figure spectrum of nanometer rods;
Fig. 4 is embodiment of the invention 1Fe
2O
3The 0.1C multiplying power cycle life curve of the lithium ion battery negative material of nanometer rods preparation;
Fig. 5 is embodiment of the invention 1Fe
2O
3The 0.5C multiplying power cycle life curve of the lithium ion battery negative material of nanometer rods preparation.
Embodiment
The present invention provides a kind of Fe
2O
3The preparation method of nanometer rods comprises the steps:
Step 1: ferro-compound and oxalates compound are dissolved in respectively in the solvent, obtain ferrous iron solution and oxalate solution, in ferrous iron solution, add a small amount of reduced iron powder, treat that frerrous chloride dissolves fully after; Put several concentrated hydrochloric acids again, prevent that ferrous iron is oxidized, become light green color to ferrous iron solution till; Oxalate solution is added in the ferrous iron solution, and constantly stir, solution is yellowing at once; Generate yellow mercury oxide, continue to stir 2h, obtain product; The mol ratio of described ferro-compound and oxalates compound is 1: 1～2, is preferably 1: 1.5, and oxalate denominationby is excessive a little to be for ferrous iron is precipitated out fully;
Step 2: product suction filtration, the washing that step 1 is obtained also places baking oven under 30-80 ℃ of condition, to dry; Desolvate and moisture to remove; Obtain dried mixture, dried mixture is ground to form the powdery thing in agate mortar, obtain compound powder;
Step 3: the compound powder that step 3 is obtained heats with 1-10 ℃/min heating rate in air, calcines 0.5-5h under the 300-700 ℃ of condition, is cooled to room temperature with 1-10 ℃/min rate of temperature fall, promptly obtains Fe
2O
3Nanometer rods.
Preferably, said ferro-compound is selected from one or both in frerrous chloride or the ferrous acetate, more preferably frerrous chloride.
Preferably, said oxalates compound is selected from one or more in oxalic acid, potassium oxalate or the ammonium oxalate, more preferably oxalic acid.
Preferably, said solvent is selected from one or more in absolute ethyl alcohol, methyl alcohol, industrial alcohol or the water, more preferably absolute ethyl alcohol.
Heating rate is preferably 2-8 ℃/min in the above-mentioned steps three, 2 ℃/min more preferably, and reaction temperature is preferably 600 ℃, and calcination time is preferably 2h, and rate of temperature fall is preferably 2-8 ℃/min, more preferably 5 ℃/min.
The present invention also provides according to above-mentioned a kind of Fe
2O
3The Fe of preparation method's preparation of nanometer rods
2O
3Nanometer rods, gained Fe
2O
3The nanometer rods size is the 30-70 nanometer, length 0.2-4 micron.
The present invention also provides above-mentioned Fe
2O
3The application of nanometer rods in the preparation lithium ion battery is with the Fe of gained
2O
3The method that the nanometer rods negative material prepares lithium ion battery is this area method commonly used, and concrete grammar is: with the negative material that makes by Fe
2O
3: the accurate weighing of mass ratio of acetylene black: PVDF (Kynoar)=70: 20: 10; Adding a certain amount of NMP (n-formyl sarcolysine base pyrrolidones) then grinds evenly; Evenly it is coated on the Copper Foil with scraper then; 120 ℃ of vacuum baking 12h are assembled into button cell then in the glove box that is being full of argon gas after the technologies such as section, compressing tablet, weighing.Used electrolyte is 1mol/L LiPF
6Ethylene carbonate+dimethyl carbonate (mass ratio is 1: 1) solution, barrier film is the celgard2400 film, and the required both positive and negative polarity battery case of assembled battery, lithium sheet, pad.
For making those skilled in the art better understand technical scheme of the present invention, the present invention is described in further detail below in conjunction with specific embodiment and accompanying drawing.
49.675g frerrous chloride and 33.75g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 60 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 600 ℃ of calcining 2h with 2 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.
With the Fe that makes
2O
3Nanometer rods is pressed Fe
2O
3: the accurate weighing of mass ratio of acetylene black: PVDF (Kynoar)=70: 20: 10; Adding a certain amount of NMP (n-formyl sarcolysine base pyrrolidones) then grinds evenly; Evenly it is coated on the Copper Foil with scraper then; 120 ℃ of vacuum baking 12h are assembled into button cell then in the glove box that is being full of argon gas after section, compressing tablet, the weighing technology, used electrolyte is 1mol/L LiPF in the battery
6Ethylene carbonate+dimethyl carbonate (mass ratio is 1: 1) solution, barrier film is the celgard2400 film, and the required both positive and negative polarity battery case of assembled battery, lithium sheet, pad.
Fig. 1 is the ferrous oxalate and the Fe of embodiment 1 preparation
2O
3The ESEM picture of nanometer rods, wherein scheming a and figure c, to be respectively multiplication factor be 10000 times of ESEM pictures with 35000 times ferrous oxalate, figure b is the Fe that multiplication factor is respectively 9000 times and 35000 times with scheming d
2O
3The ESEM picture, as can be seen from the figure, Fe
2O
3 Average grain diameter 30 nanometers, average length is 2 microns, particle diameter is even, arranges in order.
Fig. 2 is the Fe of embodiment 1 preparation
2O
3The transmission electron microscope picture of nanometer rods, as can be seen from the figure, the Fe of formation
2O
3Nanometer rods has compact texture, has effectively increased Fe in the charge and discharge process
2O
3The cycle life of negative material.
Fig. 3 is the ferrous oxalate and the Fe of the embodiment of the invention 1 preparation
2O
3The XRD figure spectrum of nanometer rods, figure a is the XRD figure spectrum of ferrous oxalate, figure b is Fe
2O
3The XRD figure spectrum of nanometer rods, test result show that above-mentioned synthetic negative material is Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact.
Fig. 4 is embodiment of the invention 1Fe
2O
3The 0.1C multiplying power cycle life curve of the lithium ion battery negative material of nanometer rods preparation, curve 1 is a discharge capacity, curve 2 is a charging capacity; As can be seen from Figure 4, after the button cell that is assembled into leaves standstill 4-5h, with the rate charge-discharge of 0.1C circulation 50 times; Its first discharge capacity be 1265mAh/g; Enclosed pasture efficient is that to maintain 95.1%, 50 its discharge capacity of circulation back be 629.2mAh/g to 71.29%, three circulation back its coulomb efficient.Show that its chemical property is good.Fig. 5 is embodiment of the invention 1Fe
2O
3The 0.5C multiplying power cycle life curve of the lithium ion battery negative material of nanometer rods preparation, curve 1 is a discharge capacity, curve 2 is a charging capacity; As can be seen from Figure 5, after the button cell that is assembled into leaves standstill 4-5h, with the rate charge-discharge of 0.5C circulation 100 times; Its first charge-discharge capacity is 1111mAh/g, and coulombic efficiency is that its coulombic efficiency maintains 96.3% after 70.52%, twice circulation; 100 times its discharge capacity of circulation back is 572.4mAh/g, shows that its chemical property is good.
Embodiment 2
49.675g frerrous chloride and 33.75g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 80 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 300 ℃ of calcining 2h with 2 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 0.2 micron of average length.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment 1, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 973.6mAh/g; 50 times circulation back capacity remains on 554.2mAh/g, shows that its chemical property is good.
Embodiment 3
49.675g frerrous chloride and 33.75g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 60 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 700 ℃ of calcining 1h with 2 ℃/min in air; 10 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 50 nanometers, 2 microns of average lengths.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment 1, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1138.3mAh/g; 50 times circulation back capacity remains on 624.1mAh/g, shows that its chemical property is good.
Embodiment 4
With 49.675g frerrous chloride and 33.75g oxalic acid be dissolved in respectively 500ml absolute ethyl alcohol and water mixed solution (V: V=1: 1), in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 3 concentrated hydrochloric acids again, become light green color to solution of ferrous chloride till, then with the alcohol of oxalic acid, water mixed solution (V: V=1: 1) add in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 80 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 600 ℃ of calcining 2h with 2 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 0.5 micron of average length.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment one, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1311.5mAh/g; 50 times circulation back capacity remains on 700.5mAh/g, shows that its chemical property is good.
Embodiment 5
49.675g frerrous chloride and 22.5g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution becomes bottle green, continues to stir 2h; Obtain small amount of precipitate thing ferrous oxalate at container bottom, with sediment ferrous oxalate filtering and washing, 80 ℃ of oven for drying; With the ferrous oxalate grind into powder in agate mortar after the oven dry; In air, be warming up to 600 ℃ of calcining 2h with 2 ℃/min, 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 2 microns of average lengths.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment one, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1270.3mAh/g; 50 times circulation back capacity remains on 631.4mAh/g, shows that its chemical property is good.
Embodiment 6
49.675g frerrous chloride and 45g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 80 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 300 ℃ of calcining 2h with 1 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is nano bar-shape Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 2 microns of average lengths.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment one, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1265.8mAh/g; 50 times circulation back capacity remains on 633.5mAh/g, shows that its chemical property is good.
Embodiment 7
43.485g ferrous acetate and 33.75g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the ferrous acetate alcoholic solution till, then the alcoholic solution of oxalic acid is added in the iron liquor; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 60 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 600 ℃ of calcining 2h with 2 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is nano bar-shape Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 2 microns of average lengths.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment one, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 982.5mAh/g; 50 times circulation back capacity remains on 703.1mAh/g, shows that its chemical property is good.
Embodiment 8
49.675g frerrous chloride and 33.75g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 1 concentrated hydrochloric acid again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 60 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 600 ℃ of calcining 0.5h with 2 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is nano bar-shape Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 0.5 micron of average length.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment one, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1164.3Ah/g; 50 times circulation back capacity remains on 705.1mAh/g, shows that its chemical property is good.
Embodiment 9
49.675g frerrous chloride and 33.75g oxalic acid are dissolved in respectively in the 500ml absolute ethyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after; Add 2 concentrated hydrochloric acids again, become light green color to the frerrous chloride alcoholic solution till, then the alcoholic solution of oxalic acid is added in the solution of ferrous chloride; And constantly stir, solution is yellowing at once, generates yellow mercury oxide; Continue to stir 2h, obtain the sediment ferrous oxalate, sediment ferrous oxalate filtering and washing; 60 ℃ of oven for drying with the ferrous oxalate grind into powder in agate mortar after the oven dry, are warming up to 600 ℃ of calcining 5h with 2 ℃/min in air; 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is nano bar-shape Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 40 nanometers, 4 microns of average lengths.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment one, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1217.4mAh/g; 50 times circulation back capacity remains on 709.3mAh/g, shows that its chemical property is good.
Embodiment 10
49.675g frerrous chloride and 37.8g oxalic acid are dissolved in respectively in the 500ml methyl alcohol, in the frerrous chloride alcoholic solution, add the 0.05g reduced iron powder, treat that frerrous chloride dissolves fully after, add 2 concentrated hydrochloric acids again; Till becoming light green color to the frerrous chloride alcoholic solution, the alcoholic solution with oxalic acid adds in the solution of ferrous chloride then, and constantly stirs, and solution is yellowing at once; Generate yellow mercury oxide, continue to stir 2h, obtain the sediment ferrous oxalate; With sediment ferrous oxalate filtering and washing, 80 ℃ of oven for drying are with the ferrous oxalate grind into powder in agate mortar after the oven dry; In air, be warming up to 600 ℃ of calcining 2h with 1 ℃/min, 5 ℃/min reduces to room temperature, promptly obtains Fe
2O
3Nanometer rods.The XRD test result shows that above-mentioned synthetic negative material is nano bar-shape Fe really
2O
3, the peak type is sharp-pointed, and the back of the body end, is smooth, and the illustrative material crystal formation is intact, Fe
2O
3Average grain diameter is 30 nanometers, 2 microns of average lengths.
With the Fe that makes
2O
3The nanometer rods negative material is assembled into button cell by the method for embodiment 1, and charge and discharge cycles is 50 times under the 0.1C multiplying power, its first discharge capacity be 1173.6mAh/g; 50 times circulation back capacity remains on 715.2mAh/g, shows that its chemical property is good.
Claims (10)
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