CN102633622B - Rodlike hydrous cupric oxalate serving as lithium ion battery cathode material and preparation method for same - Google Patents
Rodlike hydrous cupric oxalate serving as lithium ion battery cathode material and preparation method for same Download PDFInfo
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- CN102633622B CN102633622B CN201210089166.6A CN201210089166A CN102633622B CN 102633622 B CN102633622 B CN 102633622B CN 201210089166 A CN201210089166 A CN 201210089166A CN 102633622 B CN102633622 B CN 102633622B
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Abstract
The invention discloses novel rodlike hydrous cupric oxalate used for a lithium ion battery cathode and a preparation method for the rodlike hydrous cupric oxalate. The method includes: proportionally dissolving cupric chloride and oxalate which serve as raw materials into mixed solvent of ethylene glycol and water, carrying out low-temperature reaction treatment, then centrifuging and collecting precipitation so that the rodlike hydrous cupric oxalate is obtained. The synthesized rodlike hydrous cupric oxalate serving as a lithium ion battery cathode material shows good electrochemical performance, and plays a guide role in development on novel lithium ion battery materials. The method is simple and convenient in operation and easy in large-scale production and popularization.
Description
Technical field
The present invention relates to a kind of material for lithium ion battery negative and preparation method thereof, relate in particular to a kind of by solvent thermal, prepare for bar-shaped aqueous oxalic acid copper of lithium ion battery negative material and preparation method thereof; Metal nanometer material preparation and lithium ion battery field.
Background technology
In order to meet the application demand of lithium ion battery in the fields such as intelligent grid, power truck industry, military equipment and space flight, the feature that guarantee that lithium ion battery acquisition specific storage is high, have extended cycle life, security is good, development of new electrode materials is most important.For lithium ion battery negative material, negative material based on conversion reaction more and more causes numerous scholars' pass (Energy Environ.Sci., 2011,4,2682), this class material be represented as transition metal oxide, easily the transition metal oxysalt of preparation is also used as lithium ion battery negative material on this basis.
The nano material of carrying out conversion reaction is the lithium ion pond negative material of a class specific storage higher (500-1000mA.h/g).Transiting metal oxidation is the representative of this class material, France Tarascon (the Nature2000 of group, 407,496.) find and this class material is studied in detail, transition metal oxide negative material has caused numerous scholars' interest subsequently, and research finds that its operating voltage is high and cyclical stability is poor.So reduce its charge and discharge platform voltage and improve its cyclical stability and become one of focus of this research.Hispanic Tirado seminar is doing a lot of work exploring aspect this class Novel anode material, and they have found the binary metal oxide that sparking voltage is lower (Chem.Mater.2002,14,2847); First transition metal oxysalt is used for to lithium ion battery negative material subsequently, they have studied the chemical property of manganous carbonate and have carried out contrasting (Electrochem.Commun.2007,9,1744.) with its thermal decomposition product; Then carried out again the work of oxalate negative material, carried out ironic oxalate as the performance of lithium ion battery negative material and the conversion (Chem.Mater.2009 of charge and discharge process mesoxalic acid cobalt, 21,1834-1840) and the synergy (J.Mater.Chem. of binary oxalate electrode materials, 2011,21,10102) research, research finds that this class material has higher specific storage and cycle performance, but crystal water is larger to its Electrochemical Performances, before carrying out electrochemical property test, all to carry out processed.
The preparation method of oxalate is more, for example chemical precipitation method, solvent-thermal method, micro emulsion method and template.Utilize solvent-thermal method to prepare the advantage that oxalate has self, in solvent thermal reaction, one or more presomas are dissolved in solvent, and this process is relatively simple and be easy to control, and in enclosed system, can effectively prevent volatilization and the presoma of preparation to air-sensitive of toxic substance.In addition, the formation of phase, the size of particle diameter, form also can be controlled, and the dispersiveness of product is better.Under solvent thermal condition, the character of solvent (density, viscosity, dissemination) can change relatively easily, and its character has larger impact to dissolving, dispersion process and the chemical reactivity of reactant (normally solid), by the variation of solvent, can regulate and control comparatively easily the structure of product.The structure of comparing this method regulation and control product with additive method is comparatively simple and easy to do.
Also do not carry out at home at present the research of oxysalt lithium ion battery negative material, so carrying out of this work has abundant effect to the exploitation of Novel cathode material for lithium ion battery, moreover aqueous oxalic acid copper negative material can save the step of traditional oxysalt negative material processed.
Summary of the invention
For the deficiencies in the prior art, the problem to be solved in the present invention is to provide a kind of bar-shaped aqueous oxalic acid copper for lithium ion battery negative material and preparation method thereof.
Technical scheme of the present invention is to have designed a kind of easy solvent-thermal method, the mixture of ethylene glycol and water of take is solvent, take oxalic acid and cupric chloride as raw material, at room temperature cupric chloride is dissolved in mixed solvent, then adds a certain amount of oxalic acid solid, stir, after fully mixing, this mixture is transferred to in teflon-lined reactor, subzero treatment, collects and obtains aqueous oxalic acid copper powder, 100 ± 10 ℃ of vacuum-dryings; Then the aqueous oxalic acid copper that application makes and acetylene black and binding agent (mixture of Xylo-Mucine+polyvinyl alcohol) are mixed and made into electrode slice; Electrode slice is formed in glove box to button cell, at room temperature measure its charge/discharge capacity and cycle performance, using and check aqueous oxalic acid copper as the chemical property of lithium ion battery negative material.
Concrete, the bar-shaped aqueous oxalic acid copper for lithium ion battery negative material of the present invention, is characterized in that, it makes by the following method:
(1) cupric chloride of 1～10mmol being added to the volume ratio of 40mL is in the mixing solutions of the ethylene glycol of 5: 1～1: 5 and water, stirs 15～25min on magnetic stirring apparatus, cupric chloride is dissolved completely and become blue solution;
(2) in the mol ratio of oxalic acid and cupric chloride, be the ratio of 1: 1～10: 1, in the described blue solution of step (1), add oxalic acid solid, stir 20～40min, obtain blue suspension;
(3) suspension step (2) being obtained is transferred to in teflon-lined reactor, then described reactor is put into the baking oven reaction 6-24 hour of 80～150 ℃;
(4) after reaction, reactor is naturally cooled to room temperature, outwell supernatant liquor, then centrifugal, then water, ethanol respectively wash 3～5 times, obtains blue solid;
(5) blue solid step (4) being obtained is put into the baking oven vacuum-drying 24 ± 1 hours of 100 ± 10 ℃, obtains green bar-shaped aqueous oxalic acid copper powder.
Wherein: the amount of the described cupric chloride of step (1) is preferably 3mmol～6mmol.
Wherein: the volume ratio of the described ethylene glycol of step (1) and water is preferably 1: 1～and 4: 1.
Wherein: the mol ratio of the described oxalic acid of step (2) and cupric chloride is preferably 1: 1～and 4: 1.
Wherein: the described temperature of the described step of step (3) (3) is preferably 100～120 ℃, the reaction times be preferably 8 hours～12 hours.
Bar-shaped aqueous oxalic acid copper for lithium ion battery negative material of the present invention is being prepared the application of lithium ion battery with high energy density.
Further, the method for described application is:
(1) be that the ratio of 7: 2: 50 takes respectively aqueous oxalic acid copper, acetylene black and 2wt% carboxymethylcellulose sodium solution by weight, first aqueous oxalic acid copper and acetylene black are put into and in crucible, grind 15 ± 3min, then add 2wt% carboxymethylcellulose sodium solution, continue to grind 20～30min, the mixture of pasty state is coated on Copper Foil uniformly, dry at 100 ± 10 ℃, to scribbling the Copper Foil of said mixture, roll afterwards, be cut into again the certain disk of diameter, make electrode slice;
(2), in being full of the glove box of argon gas, with ordinary method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell.
With test method, at room temperature measure button cell charge/discharge capacity and the cycle performance of making, check bar-shaped aqueous oxalic acid copper as the chemical property of lithium ion battery negative material.
Test-results: loading capacity is respectively 889,494 MAhs/g for the second time for the first time, under the speed of 200mA/g, through 80 constant current charge-discharge circulations, its capacity also remains on 530 MAhs/g of left and right, has represented good cycle performance.
The present invention utilizes simple solvent-thermal method to prepare the comparatively desirable bar-shaped aqueous oxalic acid copper of chemical property, and studied first its chemical property as lithium ion battery negative material, comprise its specific storage and cycle performance, due to its good chemical property, make it in lithium ion battery field, have potential application.
The method of the bar-shaped aqueous oxalic acid copper of preparation of the present invention, easy to operation, be easy to scale operation, the bar-shaped cupric oxalate of synthesized can expand the kind of lithium ion battery negative material, overcome the low shortcoming of conventional carbon negative material specific storage, exploitation Novel cathode material for lithium ion battery is had to directive function.
Accompanying drawing explanation
Aqueous oxalic acid copper XRD figure and standard diagram that Fig. 1 is prepared.
The TEM picture of Fig. 2 aqueous oxalic acid copper.
The charge and discharge cycles figure of Fig. 3 aqueous oxalic acid copper.
Embodiment
Embodiment 1:
Take the cupric chloride of 4mmol in the beaker of 100mL, add in the mixing solutions of 20mL ethylene glycol and 20mL deionized water, on magnetic stirring apparatus, stir, when dissolving completely, cupric chloride becomes after blue solution, in this solution, add 4mmol oxalic acid solid, stir about 30min, generates blue suspension.
Then this suspension is poured in reactor, go in 100 ℃ of baking ovens and react 10h, reactor is cooled to room temperature, outwell supernatant liquor, water, ethanol is respectively washed three times, obtains blue solid, this solid vacuum-drying 24h in 100 ℃ of baking ovens has been obtained to bar-shaped aqueous oxalic acid copper powder (as figure l, Fig. 2).
Taking 0.35g aqueous oxalic acid copper and 0.1g acetylene black is put into and in crucible, grinds 10min, then add 2.5g carboxymethylcellulose sodium solution (2wt%), continue to grind 10min, the mixture of pasty state is coated on Copper Foil uniformly, then at 100 ℃, be dried 12 hours, to scribbling the Copper Foil of cobalt ferrite, roll afterwards, be cut into the disk that diameter is 12mm, make it as electrode slice.
In glove box, with ordinary method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell, with the speed of 200mA/g, on continuous current playback system, carry out electrochemical property test.Its chemical property as shown in Figure 3.
Embodiment 2:
Take the cupric chloride of 5mmol in the beaker of 100mL, add in 32mL ethylene glycol and 8mL deionized water, on magnetic stirring apparatus, stir, when dissolving completely, cupric chloride becomes after blue solution, in this solution, add 10mmol oxalic acid solid, stir about 30min, generates blue suspension.
Then this suspension is poured in reactor, gone in 120 ℃ of baking ovens and react 12h, reactor is cooled to room temperature, outwell supernatant liquor, water, ethanol is respectively washed three times, obtain blue solid, this solid vacuum-drying 24h in 100 ℃ of baking ovens has been obtained to the bar-shaped aqueous oxalic acid copper powder of superstructure.
Taking 0.35g aqueous oxalic acid copper and 0.1g acetylene black is put into and in crucible, grinds 10min, then add 2.5g carboxymethylcellulose sodium solution (2wt%), continue to grind 10min, the mixture of pasty state is coated on Copper Foil uniformly, then at 100 ℃, be dried 12h, to scribbling the Copper Foil of cobalt ferrite, roll afterwards, be cut into the disk that diameter is 12mm, make it as electrode slice.
In glove box, with ordinary method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell, with the speed of 200mA/g, on continuous current playback system, carry out electrochemical property test.
Embodiment 3:
Bar-shaped aqueous oxalic acid copper for lithium ion battery negative material makes by the following method:
(1) cupric chloride of 6mmol is added in the mixing solutions of ethylene glycol that the volume ratio of 40mL is 4: 1 and water, on magnetic stirring apparatus, stir 25min, cupric chloride is dissolved completely and become blue solution;
(2) ratio that is 4: 1 in the mol ratio of oxalic acid and cupric chloride adds oxalic acid solid in the described blue solution of step (1), stirs 30min, obtains blue suspension;
(3) suspension step (2) being obtained is transferred to 100mL with in teflon-lined reactor, and the baking oven of then described reactor being put into 120 ℃ reacts 10 hours;
(4) after reaction, reactor is naturally cooled to room temperature, outwell supernatant liquor, then centrifugal, then water, ethanol respectively wash 3 times, obtains blue solid;
(5) blue solid step (4) being obtained is put into the baking oven vacuum-drying 24 hours of 100 ℃, obtains green bar-shaped aqueous oxalic acid copper powder.
Claims (1)
1. for a bar-shaped aqueous oxalic acid copper for lithium ion battery negative material, it is characterized in that, described bar-shaped aqueous oxalic acid copper makes by the following method:
(1) cupric chloride of 1～10 mmol is added in the mixing solutions of ethylene glycol that the volume ratio of 40 mL is 5:1～1:5 and water, on magnetic stirring apparatus, stir 15～25min, cupric chloride is dissolved completely and become blue solution;
(2) ratio that is 1:1～4:1 in the mol ratio of oxalic acid and cupric chloride adds oxalic acid solid in the described blue solution of step (1), stirs 20～40min, obtains blue suspension;
(3) suspension step (2) being obtained is transferred to in teflon-lined reactor, then described reactor is put into the baking oven reaction 6-24 hour of 80～150 ℃;
(4) after reaction, reactor is naturally cooled to room temperature, outwell supernatant liquor, then centrifugal, then water, ethanol respectively wash 3～5 times, obtains blue solid;
(5) blue solid step (4) being obtained is put into the baking oven vacuum-drying 24 ± 1 hours of 100 ± 10 ℃, obtains green bar-shaped aqueous oxalic acid copper powder.
2. as claimed in claim 1 for the bar-shaped aqueous oxalic acid copper of lithium ion battery negative material, it is characterized in that: the amount of the described cupric chloride of step (1) is 3 mmol～6 mmol.
3. as claimed in claim 1 for the bar-shaped aqueous oxalic acid copper of lithium ion battery negative material, it is characterized in that: the volume ratio of the described ethylene glycol of step (1) and water is 1:1～4:1.
4. as claimed in claim 1 for the bar-shaped aqueous oxalic acid copper of lithium ion battery negative material, it is characterized in that: the described temperature of step (3) is 100～120 ℃, the reaction times is 8 hours～12 hours.
5. described in claim 1, the bar-shaped aqueous oxalic acid copper for lithium ion battery negative material is being prepared the application of lithium ion battery with high energy density.
6. application as claimed in claim 5, is characterized in that: the method for described application is:
(1) by weight taking respectively aqueous oxalic acid copper, acetylene black and 2 wt% carboxymethylcellulose sodium solutions for the ratio of 7:2:50, first aqueous oxalic acid copper and acetylene black are put into and in crucible, grind 15 ± 3 min, then add 2 wt% carboxymethylcellulose sodium solutions, continue to grind 20～30 min, the mixture of pasty state is coated on Copper Foil uniformly, dry at 100 ± 10 ℃, to scribbling the Copper Foil of said mixture, roll afterwards, be cut into again the certain disk of diameter, make electrode slice;
(2), in being full of the glove box of argon gas, with ordinary method, electrode slice, barrier film, lithium sheet and nickel foam are assembled into button cell.
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| CN104600300B (en) * | 2015-01-09 | 2017-04-12 | 贵州中伟正源新材料有限公司 | Method for preparing silicon carbide coated zinc oxalate negative material |
| CN110305005B (en) * | 2019-08-19 | 2022-02-15 | 甘肃农业大学 | Method for preparing copper oxalate based on rheological phase reaction |
| CN115504875A (en) * | 2022-10-09 | 2022-12-23 | 昆明理工大学 | Spherical-like lithium/sodium ion battery copper oxalate and negative electrode material of decomposition derivative thereof |
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| CN1935662A (en) * | 2006-10-19 | 2007-03-28 | 浙江大学 | Nano crystal constructed porous copper oxide aggregate and its preparing method |
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| CN1935662A (en) * | 2006-10-19 | 2007-03-28 | 浙江大学 | Nano crystal constructed porous copper oxide aggregate and its preparing method |
Non-Patent Citations (6)
| Title |
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| Porous Texture of CuO Prepared from Copper Oxalate Precursor;Radostin N. Nickolov et al.;《AST》;20070227;第24卷(第6期);197-506 * |
| Radostin N. Nickolov et al..Porous Texture of CuO Prepared from Copper Oxalate Precursor.《AST》.2007,第24卷(第6期),197-506. |
| 吕军军等.草酸铜及纳米氧化铜的制备与表征.《火***学报》.2011,第34卷(第1期),86-90. |
| 微乳液反应法制备草酸铜均匀微粒;甘礼华等;《物理化学学报》;19980228;第14卷(第2期);97-102 * |
| 甘礼华等.微乳液反应法制备草酸铜均匀微粒.《物理化学学报》.1998,第14卷(第2期),97-102. |
| 草酸铜及纳米氧化铜的制备与表征;吕军军等;《火***学报》;20110228;第34卷(第1期);86-90 * |
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