CN102502789B - Alkaline earth metal germanate nanomaterial and preparation method thereof and use thereof as cathode material of lithium ion battery - Google Patents
Alkaline earth metal germanate nanomaterial and preparation method thereof and use thereof as cathode material of lithium ion battery Download PDFInfo
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Abstract
The invention discloses an alkaline earth metal germanate nanomaterial and a preparation method thereof and use of the nanomaterial as a cathode material of lithium ion batteries. The method comprises the following steps of: (1) mixing an aqueous solution of alkaline earth metal salt and germanium source compound GeO2 to obtain a liquid mixture; (2) allowing reaction of the liquid mixture obtained in the step (1) to take place in a polytetrafluoroethylene-lined high-pressure reaction kettle after heating, and cooling after the reaction is completed to obtain the alkaline earth metal germanate nanomaterial. The method is simple, has abundant and easily-available raw materials, is suitable for large-scale production and has a high level of practicability. The obtained alkaline earth metal germanate is a nanomaterial, has a high actual capacity, can be directly used as a cathode material of lithium ion batteries, solves the problem that the germanium-based material as lithium ion battery cathode material has a poor cycling property and takes a violent change of volume during charging/discharging process, and can be directly used as the cathode material of lithium ion batteries.
Description
Technical field
The present invention relates to alkaline-earth metal germanate nano material and preparation method thereof and application as lithium ion battery negative material.
Background technology
Along with the high speed development in the fields such as the energy, traffic, information, national defence, the performance of energy storage device is had higher requirement.Lithium ion battery has the ideal source that the outstanding advantages such as operating voltage is high, energy density is high, capacity is large, self discharge is little, cyclicity is good, long service life, lightweight, volume is little become the portable electric appts such as notebook computer, panel computer, mobile phone because of it.In order to meet the actual operation requirements such as safety, stable, stand-by time is long, high power capacity, extended-life lithium ion battery become an important research direction of its development.Because the specific capacity of positive electrode current material is relatively low, the room for promotion of capacity is little, therefore the development work of high-capacity lithium ion cell mainly concentrates on negative material.Therefore at present, commercial used negative material is material with carbon element, and its theoretical specific capacity only has 372mAh/g, and finding the high power capacity negative material that can substitute carbon becomes an important research direction.
Germanium has high theoretical specific capacity (1600mAh/g), higher lithium ion mobility and conductivity, and widely distributed in the earth, therefore cost is lower, environmental sound, becomes a kind of promising negative material.Yet in charge and discharge process, the removal lithium embedded process of germanium is followed 370% change in volume, cause that electrode cracking and active material come off from collector, structure is efflorescence destruction gradually, thereby cause capacity in cyclic process repeatedly constantly to decline.For this problem, mainly by the following aspects, improve in recent years the cyclicity of germanium negative material:
1, nano simple substance germanium material
In order to improve the cycle performance of elemental Germanium, germanium nanometer can be fallen to a certain extent and reduced its change in volume, reduce electrode interior stress.Although Ge nanoline, Ge nano-tube etc. be volume meeting dilation in charge and discharge process, length and diameter also can change, but one dimension Ge nanoline or pipe be the variation of buffer volumes effectively, structure in repeated charge process is not broken, electronics can flow to nano wire or pipe from collector effectively simultaneously, and the electrolyte of nano wire or the infiltration of pipe Clearance Between Wound has shortened the path of lithium ion diffusion, makes it have good cyclicity and high-multiplying power discharge.Yet although the cyclicity of Ge nanoline, nanotube is better, its preparation process is complicated, yields poorly, and cost of material is high, only limits at present phase of basic research, is difficult to large-scale industrialization and produces, and degree of being practical is low.
2, germanium based composites
Current research germanium based composites mainly concentrates on germanium-carbon composite.Because carbon has good flexibility, good electron conduction, less density, less volumetric expansion (10%), therefore become the active matrix of germanium base negative material.Germanium surface carry out carbon coated after, can effectively prevent elemental Germanium oxidation, reduce irreversible capacity, also cushion the change in volume in charge and discharge process simultaneously, prevent reunion and the growth of germanium particle, thereby improve the Capacitance reserve performance of germanium base negative material.But also there are some problems in germanium carbon composite, during preparation, conventionally adopt vapour deposition process and polymerization-pyrolysismethod etc., the same preparation process of these methods is complicated, yields poorly, and is difficult to large-scale production.
Except adopting above-mentioned germanium-carbon composite, also there is the compound of research employing germanium, for example germanium dioxide (GeO
2), germanium disulfide (GeS
2), phosphoric acid germanium lithium (LiGe
2(PO
4)
3) as negative material, they can form germanium particle and be embedded in Li in the process discharging and recharging for the first time
2o, Li
2s, Li
3pO
4in base matter, play equally the effect that buffer volumes changes, but cyclicity still can not meet actual requirement, and specific capacity is low.Therefore the germanium base nanometer anode material that, develops a kind of high-performance and be suitable for large-scale production has very important significance to the development of high performance lithium ion battery.
Summary of the invention
The object of this invention is to provide a kind of alkaline-earth metal germanate nano material and preparation method thereof and application as lithium ion battery negative material.
The method of preparing alkaline-earth metal germanate nano material provided by the invention, comprises the steps:
1) by the aqueous solution of alkali salt and germanium source compound GeO
2mix and obtain mixed liquor;
2) by step 1) gained mixed liquor reacts after heating up in teflon-lined reactor, reacts complete cooling, obtains described alkaline-earth metal germanate nano material.
In said method, described alkali salt is selected from acetate and at least one in hydroxide: Mg, Ca, Sr and the Ba of following metallic element; Described alkali salt and GeO
2the ratio of the amount of substance that feeds intake be 1: 4-10: 1; Wherein, for calcium salt and GeO
2the amount of substance that feeds intake than preferably 2: 7-2: 1, specifically can be 2: 7-1: 1 or 1: 1-2: 1; For strontium salt and GeO
2the ratio preferably 1 of the amount of substance that feeds intake: 4-2: 1, specifically can be 1: 4-1: 2 or 1: 2-2: 1; For barium salt and GeO
2the amount of substance that feeds intake than preferably 5: 1-10: 1, specifically can be 5: 1-7: 1 or 7: 1-10: 1; For magnesium salts and GeO
2the ratio preferably 1 of the amount of substance that feeds intake: 1-5: 1, specifically can be 1: 1-2: 1 or 2: 1-5: 1.The concentration of the aqueous solution of described alkali salt is as the criterion to dissolve alkali salt completely.
Described step 3) in, in described heating step, heating rate is 5-30 ℃/min, specifically can be 5-20 ℃/min, 5-10 ℃/min, 10-30 ℃/min, 10-20 ℃/min or 20-30 ℃/min; In described reactions steps, temperature is 180 ℃-200 ℃, specifically can be 180-190 ℃ or 190-200 ℃, and the time is 12-48 hour, specifically can be 12-24 hour, 12-36 hour, 24-48 hour, 24-36 hour or 36-48 hour; Described teflon-lined volume is 25mL-100mL, specifically can be 25mL-50mL or 50-100mL; In described cooling step, the type of cooling can be and naturally cools to room temperature.
In addition, said method also comprises the steps: after completion of the reaction described, and cooling rear gained reaction system is washed with deionized water, dry after centrifugation, can obtain pure described alkaline-earth metal germanate nano material.
The alkaline-earth metal germanate nano material preparing according to the method described above, also belongs to protection scope of the present invention.Described alkaline-earth metal germanate nano material is at least one in alkaline-earth metal germanic acid magnesium nano material, alkaline-earth metal calcium germinate nano material, alkaline-earth metal germanic acid strontium nano material and alkaline-earth metal germanic acid barium nano material;
Wherein, in described alkaline-earth metal germanic acid magnesium nano material, the apparent physical state of described germanic acid magnesium is germanic acid magnesium nanometer sheet, and the diameter of described nanometer sheet is 2-10 μ m, and thickness is 20-80nm;
The apparent physical state of described calcium germinate is calcium germinate one-dimensional nano line, and the length of described calcium germinate one-dimensional nano line is 20-1000 μ m, and diameter is 20-70nm;
The apparent physical state of described germanic acid strontium is germanic acid strontium one-dimensional nano line, and the length of described germanic acid strontium one-dimensional nano line is 50-1000 μ m, and diameter is 20-80nm;
The apparent physical state of described germanic acid barium is germanic acid barium one-dimensional nano line, and the length of described germanic acid barium one-dimensional nano line is 50-500 μ m, and diameter is 20-60nm.
The alkaline-earth metal germanate nano material that the invention described above provides is as the application of battery electrode material, and the energy storage elements or the portable electric appts that contain described alkaline-earth metal germanate nano material, also belongs to protection scope of the present invention.Wherein, described battery electrode material is preferably lithium ion battery negative material; Described stored energy original paper is preferably lithium ion battery negative material; Described portable electric appts is mobile phone, camera, video camera, MP3, MP4 or notebook computer.
Compared with prior art, the method technique of preparing alkaline-earth metal germanate nano material provided by the invention is simple, and raw material is easy to get, and output is high, suitable for mass production, and degree of being practical is high.And the alkaline-earth metal germanate obtaining is nano material, improved the cyclicity that germanium material exists as lithium ion battery negative material poor, the violent problem of stereomutation in charge and discharge process, can be directly as the electrode material use of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the calcium germinate nano material that obtains of embodiment 1.
Fig. 2 is the electron scanning micrograph of the calcium germinate nano material that obtains of embodiment 1.
Fig. 3 is that the calcium germinate nano material that embodiment 1 obtains is negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
Fig. 4 is X-ray diffraction (XRD) collection of illustrative plates of the germanic acid strontium nano material that obtains of embodiment 4.
Fig. 5 is the electron scanning micrograph of the germanic acid strontium nano material that obtains of embodiment 4.
Fig. 6 is that the germanic acid strontium nano material that embodiment 4 obtains is negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
Fig. 7 is X-ray diffraction (XRD) collection of illustrative plates of the germanic acid barium nano material that obtains of embodiment 7.
Fig. 8 is the electron scanning micrograph of the germanic acid barium nano material that obtains of embodiment 7.
Fig. 9 is that the germanic acid barium nano material that embodiment 7 obtains is negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
Figure 10 is X-ray diffraction (XRD) collection of illustrative plates of the germanic acid magnesium nano material that obtains of embodiment 10.
Figure 11 is the electron scanning micrograph of the germanic acid magnesium nano material that obtains of embodiment 10.
Figure 12 is that the germanic acid magnesium nano material that embodiment 10 obtains is negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
The preparation of embodiment 1, calcium germinate nano material and electrochemical property test thereof
According to Ca (CH
3cOO)
2h
2o: GeO
2the ratio of=2: 7 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 25mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 10 ℃/min, from room temperature, rise to 180 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The sign of calcium germinate nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αray) Analysis deterrmination structure, result as shown in Figure 1.As can be seen from the figure, not having impurity peaks in spectrogram, illustrate that product purity is high, is target product calcium germinate.
With NEC ESEM (JEOL-6700F), detect length and the diameter of the calcium germinate obtaining under above-mentioned condition, result shows that resulting calcium germinate is 1-dimention nano line structure, and length is at 20-1000 μ m, and diameter is at 20-70nm (being shown in Fig. 2).
The Electrochemical Characterization of calcium germinate:
The calcium germinate preparing in embodiment 1, acetylene black and Kynoar (binding agent) are mixed and are made into slurry with mass ratio at 70: 20: 10, be coated to equably on Copper Foil collector and obtain cathode membrane.Using metal lithium sheet as positive pole, and microporous polypropylene membrane (Celgard 2400) is as barrier film, 1mol/L LiPF
6(solvent is that volume ratio is ethylene carbonate and the dimethyl carbonate mixed liquor of 1: 1), as electrolyte, is assembled into Swagelok type simulated battery in the glove box of argon shield.
The battery of above-mentioned assembling is carried out to constant current charge-discharge test on Arbin BT2000 charge-discharge test instrument, and charge-discharge magnification is 100mA/g, and charging/discharging voltage interval is 0-3.0V, and charging and discharging curve is shown in Fig. 3.The calcium germinate preparing in the present embodiment and simulated battery test result are listed in table 1.
The preparation of embodiment 2, calcium germinate nano material and electrochemical property test thereof
According to Ca (OH)
2: GeO
2the ratio of=1: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 50mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 20 ℃/min, from room temperature, rise to 200 ℃, and keep 48 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 1.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the calcium germinate preparing in the present embodiment and simulated battery test result are listed in table 1.
The preparation of embodiment 3, calcium germinate nano material and electrochemical property test thereof
According to Ca (CH
3cOO)
2h
2o: GeO
2the ratio of=2: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 25mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 30 ℃/min, from room temperature, rise to 200 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 1.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the calcium germinate preparing in the present embodiment and simulated battery test result are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 4, germanic acid strontium nano material
According to Sr (CH
3cOO)
21/2H
2o: GeO
2the ratio of=1: 4 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 25mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 5 ℃/min, from room temperature, rise to 180 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The sign of germanic acid strontium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αray) Analysis deterrmination structure, result as shown in Figure 4.As can be seen from the figure, not having impurity peaks in spectrogram, illustrate that product purity is high, is target product germanic acid strontium.
With NEC ESEM (JEOL-6700F), detect length and the diameter of the germanic acid strontium obtaining under above-mentioned condition, result shows that resulting germanic acid strontium is 1-dimention nano line structure, and length is at 50-1000 μ m, and diameter is at 20-80nm (being shown in Fig. 5).
The Electrochemical Characterization of germanic acid strontium:
Germanic acid strontium, acetylene black and the Kynoar (binding agent) that in embodiment 4, prepare are mixed and are made into slurry with mass ratio at 70: 20: 10, be coated to equably on Copper Foil collector and obtain cathode membrane.Using metal lithium sheet as positive pole, and microporous polypropylene membrane (Celgard 2400) is as barrier film, 1mol/L LiPF
6(solvent is that volume ratio is ethylene carbonate and the dimethyl carbonate mixed liquor of 1: 1), as electrolyte, is assembled into Swagelok type simulated battery in the glove box of argon shield.
The battery of above-mentioned assembling is carried out to constant current charge-discharge test on Arbin BT2000 charge-discharge test instrument, and charge-discharge magnification is 100mA/g, and charging/discharging voltage interval is 0-3.0V, and charging and discharging curve is shown in Fig. 6.The germanic acid strontium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 5, germanic acid strontium nano material
According to Sr (OH)
28H
2o: GeO
2the ratio of=1: 2 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 100mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 30 ℃/min, from room temperature, rise to 200 ℃, and keep 12 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 4.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 4, and the germanic acid strontium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 6, germanic acid strontium nano material
According to Sr (CH
3cOO)
21/2H
2o: GeO
2the ratio of=2: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 50mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 10 ℃/min, from room temperature, rise to 190 ℃, and keep 48 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 4.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 4, and the germanic acid strontium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 7, germanic acid barium nano material
According to Ba (CH
3cOO)
2h
2o: GeO
2the ratio of=10: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 25mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 10 ℃/min, from room temperature, rise to 180 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The sign of germanic acid barium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αray) Analysis deterrmination structure, result as shown in Figure 7.As can be seen from the figure, not having impurity peaks in spectrogram, illustrate that product purity is high, is target product germanic acid barium.
With NEC ESEM (JEOL-6700F), detect length and the diameter of the germanic acid barium obtaining under above-mentioned condition, result shows that resulting germanic acid barium is 1-dimention nano line structure, and length is at 50-500 μ m, and diameter is at 20-60nm (being shown in Fig. 8).
The Electrochemical Characterization of germanic acid barium:
Germanic acid barium, acetylene black and the Kynoar (binding agent) that in embodiment 7, prepare are mixed and are made into slurry with mass ratio at 70: 20: 10, be coated to equably on Copper Foil collector and obtain cathode membrane.Using metal lithium sheet as positive pole, and microporous polypropylene membrane (Celgard 2400) is as barrier film, 1mol/L LiPF
6(solvent is that volume ratio is ethylene carbonate and the dimethyl carbonate mixed liquor of 1: 1), as electrolyte, is assembled into Swagelok type simulated battery in the glove box of argon shield.
The battery of above-mentioned assembling is carried out to constant current charge-discharge test on Arbin BT2000 charge-discharge test instrument, and charge-discharge magnification is 100mA/g, and charging/discharging voltage interval is 0-3.0V, and charging and discharging curve is shown in Fig. 9.The germanic acid barium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 8, germanic acid barium nano material
According to Ba (CH
3cOO)
2h
2o: GeO
2the ratio of=7: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 50mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 20 ℃/min, from room temperature, rise to 180 ℃, and keep 36 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 7.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 7, and the germanic acid barium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 9, germanic acid barium nano material
According to Ba (OH)
28H
2o: GeO
2the ratio of=5: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 100mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 30 ℃/min, from room temperature, rise to 190 ℃, and keep 48 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 7.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 7, and the germanic acid barium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 10, germanic acid magnesium nano material
According to Mg (CH
3cOO)
24H
2o: GeO
2the ratio of=1: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 25mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 10 ℃/min, from room temperature, rise to 180 ℃, and keep 48 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The sign of germanic acid magnesium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αray) Analysis deterrmination structure, result as shown in figure 10.As can be seen from the figure, not having impurity peaks in spectrogram, illustrate that product purity is high, is target product germanic acid magnesium.
With NEC ESEM (JEOL-6700F), detect thickness and the diameter of the germanic acid magnesium obtaining under above-mentioned condition, result shows that resulting germanic acid magnesium is nano flake structure, and diameter is at 2-10 μ m, and thickness is at 20-80nm (being shown in Figure 11).
The Electrochemical Characterization of germanic acid magnesium:
Germanic acid magnesium, acetylene black and the Kynoar (binding agent) that in embodiment 10, prepare are mixed and are made into slurry with mass ratio at 70: 20: 10, be coated to equably on Copper Foil collector and obtain cathode membrane.Using metal lithium sheet as positive pole, and microporous polypropylene membrane (Celgard 2400) is as barrier film, 1mol/L LiPF
6(solvent is that volume ratio is ethylene carbonate and the dimethyl carbonate mixed liquor of 1: 1), as electrolyte, is assembled into Swagelok type simulated battery in the glove box of argon shield.
The battery of above-mentioned assembling is carried out to constant current charge-discharge test on Arbin BT2000 charge-discharge test instrument, and charge-discharge magnification is 100mA/g, and charging/discharging voltage interval is 0-3.0V.The germanic acid magnesium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 11, germanic acid magnesium nano material
According to Mg (CH
3cOO)
24H
2o: GeO
2the ratio of=2: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 50mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 20 ℃/min, from room temperature, rise to 180 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 10.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 10, and the germanic acid barium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
Preparation and the electrochemical property test thereof of embodiment 12, germanic acid magnesium nano material
According to Mg (OH)
2: GeO
2the ratio of=5: 1 amount of substance takes, ultrasonic agitation 30min in water, after mixing, transfer in the autoclave liner of 100mL polytetrafluoroethylene, put it in stainless steel autoclave, with the heating rate of 30 ℃/min, from room temperature, rise to 200 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder.
The structural confirmation result of this white powder and apparent physical aspect, length and diameter are all identical with embodiment 10.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 10, and the germanic acid barium and the simulated battery test result that in the present embodiment, prepare are listed in table 1.
The preparation condition of table 1, alkaline-earth metal germanate nano material and simulated battery test result
According to the result of table 1, can find out, the present invention uses soluble alkaline earth salt and germanium dioxide, through water under high pressure thermal response, can conveniently prepare alkaline-earth metal germanate nano material.As a kind of negative material of novel lithium ion battery, improved to a great extent the poor problem of cycle performance that germanium base negative material exists, shown higher specific capacity.
Claims (1)
1. a method of preparing germanic acid strontium nano material, comprises the steps: (the CH according to Sr
3cOO)
21/2H
2o:GeO
2the ratio of the amount of substance of=1:4 takes, ultrasonic agitation 30min in water, transfers to after mixing in the autoclave liner of 25mL polytetrafluoroethylene, puts it in stainless steel autoclave, heating rate with 5 ℃/min, from room temperature, rise to 180 ℃, and keep 24 hours, then naturally cool to room temperature, with deionized water washing three times, dry after centrifugation, obtain white powder, be described germanic acid strontium nano material.
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| CN103224250B (en) * | 2013-05-15 | 2014-07-23 | 东华大学 | Preparation method of copper germanate quantum dots |
| CN103754928A (en) * | 2014-01-08 | 2014-04-30 | 安徽工业大学 | Preparation method of vanadium doped germanate nanowire |
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