CN102502789A - 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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- CN102502789A CN102502789A CN2011103110936A CN201110311093A CN102502789A CN 102502789 A CN102502789 A CN 102502789A CN 2011103110936 A CN2011103110936 A CN 2011103110936A CN 201110311093 A CN201110311093 A CN 201110311093A CN 102502789 A CN102502789 A CN 102502789A
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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 earth alkali 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 fields such as the energy, traffic, information, national defence, to the demands for higher performance of energy storage device.Lithium ion battery is because of it has that WV height, energy density are high, capacity is big, self-discharge is little, cyclicity is good, the ideal source of long service life, in light weight, outstanding advantage becomes portable electric appts such as notebook computer, panel computer, mobile telephone such as volume is little.For actual request for utilizations such as satisfying safely, stablize, standby time is long, heavy body, extended-life lithium ion battery become a research direction of its development.Because the specific storage of positive electrode current material is relatively low, the room for promotion of capacity is little, so the development work of high-capacity lithium ion cell mainly concentrates on negative material.At present, commercial employed negative material is a carbon material, and its theoretical specific capacity only has 372mAh/g, and therefore seeking the heavy body negative material that can substitute carbon becomes an important research direction.
Germanium has high theoretical specific capacity (1600mAh/g), and therefore higher lithium ion mobility and specific conductivity, and in the earth, distribute extensive, lower, the environmental sound of cost become a kind of promising negative material.Yet in charge and discharge process, the removal lithium embedded process of germanium is followed 370% volume change, causes that electrode cracking and active substance come off from collector, and structure is efflorescence destruction gradually, thereby causes that capacity constantly descends in working cycle repeatedly.To this problem, mainly improve the cyclicity of germanium negative material in recent years through the following aspects:
1, nano simple substance germanium material
In order to improve the cycle performance of elemental Germanium, the germanium nanometer can be fallen to a certain extent reduce its volume change, reduce electrode interior stress.The contraction although volume in charge and discharge process such as Ge nanoline, Ge nano-tube can expand; Length and diameter also can change; But one dimension Ge nanoline or the effectively variation of buffer volumes of pipe make that structure is not broken in the repeated charge process, and electronics can flow to nano wire or pipe from collector effectively simultaneously; And the electrolytic solution that nano wire or pipe twine the gap infiltration has shortened the path that lithium ion spreads, and makes it have good cyclicity and high-multiplying power discharge property.Although yet the cyclicity of Ge nanoline, nanotube is better, its preparation process is complicated, yields poorly, and raw materials cost is high, only limits to the fundamental research stage at present, is difficult to large-scale industrialization production, and degree of being practical is low.
2, germanium based composites
Present research germanium based composites mainly concentrates on germanium-carbon composite.Flexibility, good electron electroconductibility, less density, smaller volume expand (10%) because carbon has preferably, therefore become the active matrix of germanium base negative material.After the carbon coating is carried out on the germanium surface, can effectively prevent the elemental Germanium oxidation, reduce irreversible capacity, also cushion the volume change in the charge and discharge process simultaneously, prevent that the germanium particulate from reuniting and growth, thereby the capacity of raising germanium base negative material keeps performance.But also there are some problems in the germanium carbon composite, adopts vapour deposition process and polymerization-pyrogenic silica etc. during preparation usually, and these methods prepare the process complicacy equally, yield poorly, and are difficult to large-scale production.
Except adopting above-mentioned germanium-carbon composite, also there is research to adopt the compound of 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 the germanium particle in the first time in the charging and discharging process and be embedded in Li
2O, Li
2S, Li
3PO
4In base matter, play the effect that buffer volumes changes equally, but cyclicity still can not satisfy actual requirement, and specific storage is low.Therefore, the germanium Ji Nami negative material that develops a kind of high-performance and be suitable for scale operation has very important significance to the development of high performance lithium ion battery.
Summary of the invention
The purpose of this invention is to provide a kind of earth alkali metal germanate nano material and preparation method thereof and application as lithium ion battery negative material.
The method for preparing earth alkali metal germanate nano material provided by the invention comprises the steps:
1) with the aqueous solution and the germanium source compound GeO of alkaline earth salt
2Mixing obtains mixed solution;
2) react after step 1) gained mixed solution is heated up in the teflon-lined reaction kettle, the reaction cooling that finishes obtains said earth alkali metal germanate nano material.
In the aforesaid method, said alkaline earth salt is selected from least a in acetate and the oxyhydroxide of following metallic element: Mg, Ca, Sr and Ba; Said alkaline earth 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 preferred 2: 7-2: 1, specifically can be 2: 7-1: 1 or 1: 1-2: 1; For strontium salt and GeO
2The ratio preferred 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 preferred 5: 1-10: 1, specifically can be 5: 1-7: 1 or 7: 1-10: 1; For magnesium salts and GeO
2The ratio preferred 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 said alkaline earth salt is as the criterion to dissolve alkaline earth salt fully.
In the said step 3), in the said heating step, temperature rise 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 the said reactions step, 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; Said teflon-lined volume is 25mL-100mL, specifically can be 25mL-50mL or 50-100mL; In the said cooling step, the type of cooling can be and naturally cools to room temperature.
In addition, aforesaid method also comprises the steps: after said reaction finishes, and will cool off back gained reaction system and use deionized water wash, and the spinning after drying can obtain purified said earth alkali metal germanate nano material.
The earth alkali metal germanate nano material for preparing according to the method described above also belongs to protection scope of the present invention.Said earth alkali metal germanate nano material is at least a in earth alkali metal germanic acid magnesium nano material, earth alkali metal germanic acid calcium nano material, earth alkali metal germanic acid strontium nano material and the earth alkali metal germanic acid barium nano material;
Wherein, in the said earth alkali metal germanic acid magnesium nano material, the apparent physical condition of said germanic acid magnesium is a germanic acid magnesium nanometer sheet, and the diameter of said nanometer sheet is 2-10 μ m, and thickness is 20-80nm;
The apparent physical condition of said germanic acid calcium is a germanic acid calcium one-dimensional nano line, and the length of said germanic acid calcium one-dimensional nano line is 20-1000 μ m, and diameter is 20-70nm;
The apparent physical condition of said germanic acid strontium is a germanic acid strontium one-dimensional nano line, and the length of said germanic acid strontium one-dimensional nano line is 50-1000 μ m, and diameter is 20-80nm;
The apparent physical condition of said germanic acid barium is a germanic acid barium one-dimensional nano line, and the length of said germanic acid barium one-dimensional nano line is 50-500 μ m, and diameter is 20-60nm.
The earth alkali 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 said earth alkali metal germanate nano material, also belongs to protection scope of the present invention.Wherein, said battery electrode material is preferably lithium ion battery negative material; Said energy storage original paper is preferably lithium ion battery negative material; Said portable electric appts is mobile telephone, photographic camera, pick up camera, MP3, MP4 or notebook computer.
Compared with prior art, the method technology for preparing earth alkali 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 earth alkali metal germanate that obtains is a nano material, and it is poor as the cyclicity that lithium ion battery negative material exists to have improved germanium material, the violent problem of stereomutation in the charge and discharge process, can be directly as the electrode materials use of lithium ion battery.
Description of drawings
X-ray diffraction (XRD) collection of illustrative plates of the germanic acid calcium nano material that Fig. 1 obtains for embodiment 1.
The electron scanning micrograph of the germanic acid calcium nano material that Fig. 2 obtains for embodiment 1.
The germanic acid calcium nano material that Fig. 3 obtains for embodiment 1 is a negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
X-ray diffraction (XRD) collection of illustrative plates of the germanic acid strontium nano material that Fig. 4 obtains for embodiment 4.
The electron scanning micrograph of the germanic acid strontium nano material that Fig. 5 obtains for embodiment 4.
The germanic acid strontium nano material that Fig. 6 obtains for embodiment 4 is a negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
X-ray diffraction (XRD) collection of illustrative plates of the germanic acid barium nano material that Fig. 7 obtains for embodiment 7.
The electron scanning micrograph of the germanic acid barium nano material that Fig. 8 obtains for embodiment 7.
The germanic acid barium nano material that Fig. 9 obtains for embodiment 7 is a negative material, the charging and discharging curve of first three circle under 100mA/g constant current charge-discharge condition.
X-ray diffraction (XRD) collection of illustrative plates of the germanic acid magnesium nano material that Figure 10 obtains for embodiment 10.
The electron scanning micrograph of the germanic acid magnesium nano material that Figure 11 obtains for embodiment 10.
The germanic acid magnesium nano material that Figure 12 obtains for embodiment 10 is a 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 done further elaboration, but the present invention is not limited to following examples.Said method is ordinary method if no special instructions.Said material all can get from open commercial sources if no special instructions.
The preparation and the electrochemical property test thereof of embodiment 1, germanic acid calcium nano material
According to Ca (CH
3COO)
2H
2O: GeO
2The ratio of=2: 7 amount of substance takes by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 25mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 180 ℃ from room temperature with the temperature rise rate of 10 ℃/min; And kept 24 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains white powder.
The sign of germanic acid calcium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) analyze definite structure, the result is as shown in Figure 1.As can be seen from the figure, there is not impurity peaks in the spectrogram, explains that product purity is high, is title product germanic acid calcium.
With the length and the diameter of the germanic acid calcium that obtains under the above-mentioned condition of NEC's ESEM (JEOL-6700F) detection, the result shows that resulting germanic acid calcium is the 1-dimention nano line structure, and length is at 20-1000 μ m, and diameter is in the 20-70nm (see figure 2).
The chemical property of germanic acid calcium characterizes:
Germanic acid calcium, acetylene black and the pvdf (sticker) that prepare among the embodiment 1 are made into slurry with mass ratio mixing in 70: 20: 10, are coated to equably on the Copper Foil collector and obtain cathode membrane.As positive pole, microporous polypropylene membrane (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6(solvent is that volume ratio is 1: 1 NSC 11801 and a methylcarbonate mixed solution) is assembled into the Swagelok pattern and intends battery as electrolytic solution in the glove box of argon shield.
The battery of above-mentioned assembling is carried out the constant current charge-discharge test on Arbin BT2000 charge-discharge test appearance, charge-discharge magnification is 100mA/g, and the charging/discharging voltage interval is 0-3.0V, and charging and discharging curve is seen Fig. 3.The germanic acid calcium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The preparation and the electrochemical property test thereof of embodiment 2, germanic acid calcium nano material
According to Ca (OH)
2: GeO
2The ratio of=1: 1 amount of substance takes by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 50mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 200 ℃ from room temperature with the temperature rise rate of 20 ℃/min; And kept 48 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 1, and the germanic acid calcium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The preparation and the electrochemical property test thereof of embodiment 3, germanic acid calcium nano material
According to Ca (CH
3COO)
2H
2O: GeO
2The ratio of=2: 1 amount of substance takes by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 25mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 200 ℃ from room temperature with the temperature rise rate of 30 ℃/min; And kept 24 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 1, and the germanic acid calcium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 25mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 180 ℃ from room temperature with the temperature rise rate of 5 ℃/min; And kept 24 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains white powder.
The sign of germanic acid strontium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) analyze definite structure, the result is as shown in Figure 4.As can be seen from the figure, there is not impurity peaks in the spectrogram, explains that product purity is high, is title product germanic acid strontium.
With the length and the diameter of the germanic acid strontium that obtains under the above-mentioned condition of NEC's ESEM (JEOL-6700F) detection, the result shows that resulting germanic acid strontium is the 1-dimention nano line structure, and length is at 50-1000 μ m, and diameter is in the 20-80nm (see figure 5).
The chemical property of germanic acid strontium characterizes:
Germanic acid strontium, acetylene black and the pvdf (sticker) that prepare among the embodiment 4 are made into slurry with mass ratio mixing in 70: 20: 10, are coated to equably on the Copper Foil collector and obtain cathode membrane.As positive pole, microporous polypropylene membrane (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6(solvent is that volume ratio is 1: 1 NSC 11801 and a methylcarbonate mixed solution) is assembled into the Swagelok pattern and intends battery as electrolytic solution in the glove box of argon shield.
The battery of above-mentioned assembling is carried out the constant current charge-discharge test on Arbin BT2000 charge-discharge test appearance, charge-discharge magnification is 100mA/g, and the charging/discharging voltage interval is 0-3.0V, and charging and discharging curve is seen Fig. 6.The germanic acid strontium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 100mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 200 ℃ from room temperature with the temperature rise rate of 30 ℃/min; And kept 12 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 4, and the germanic acid strontium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 50mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 190 ℃ from room temperature with the temperature rise rate of 10 ℃/min; And kept 48 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 4, and the germanic acid strontium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 25mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 180 ℃ from room temperature with the temperature rise rate of 10 ℃/min; And kept 24 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains white powder.
The sign of germanic acid barium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) analyze definite structure, the result is as shown in Figure 7.As can be seen from the figure, there is not impurity peaks in the spectrogram, explains that product purity is high, is title product germanic acid barium.
With the length and the diameter of the germanic acid barium that obtains under the above-mentioned condition of NEC's ESEM (JEOL-6700F) detection, the result shows that resulting germanic acid barium is the 1-dimention nano line structure, and length is at 50-500 μ m, and diameter is in the 20-60nm (see figure 8).
The chemical property of germanic acid barium characterizes:
Germanic acid barium, acetylene black and the pvdf (sticker) that prepare among the embodiment 7 are made into slurry with mass ratio mixing in 70: 20: 10, are coated to equably on the Copper Foil collector and obtain cathode membrane.As positive pole, microporous polypropylene membrane (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6(solvent is that volume ratio is 1: 1 NSC 11801 and a methylcarbonate mixed solution) is assembled into the Swagelok pattern and intends battery as electrolytic solution in the glove box of argon shield.
The battery of above-mentioned assembling is carried out the constant current charge-discharge test on Arbin BT2000 charge-discharge test appearance, charge-discharge magnification is 100mA/g, and the charging/discharging voltage interval is 0-3.0V, and charging and discharging curve is seen Fig. 9.The germanic acid barium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 50mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 180 ℃ from room temperature with the temperature rise rate of 20 ℃/min; And kept 36 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 7, and the germanic acid barium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 100mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 190 ℃ from room temperature with the temperature rise rate of 30 ℃/min; And kept 48 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 7, and the germanic acid barium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 25mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 180 ℃ from room temperature with the temperature rise rate of 10 ℃/min; And kept 48 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains white powder.
The sign of germanic acid magnesium nano material:
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) analyze definite structure, the result is shown in figure 10.As can be seen from the figure, there is not impurity peaks in the spectrogram, explains that product purity is high, is title product germanic acid magnesium.
With the thickness and the diameter of the germanic acid magnesium that obtains under the above-mentioned condition of NEC's ESEM (JEOL-6700F) detection, the result shows that resulting germanic acid magnesium is the nano flake structure, and diameter is at 2-10 μ m, and thickness is at 20-80nm (seeing Figure 11).
The chemical property of germanic acid magnesium characterizes:
Germanic acid magnesium, acetylene black and the pvdf (sticker) that prepare among the embodiment 10 are made into slurry with mass ratio mixing in 70: 20: 10, are coated to equably on the Copper Foil collector and obtain cathode membrane.As positive pole, microporous polypropylene membrane (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6(solvent is that volume ratio is 1: 1 NSC 11801 and a methylcarbonate mixed solution) is assembled into the Swagelok pattern and intends battery as electrolytic solution in the glove box of argon shield.
The battery of above-mentioned assembling is carried out the constant current charge-discharge test on Arbin BT2000 charge-discharge test appearance, charge-discharge magnification is 100mA/g, and the charging/discharging voltage interval is 0-3.0V.The germanic acid magnesium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 50mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 180 ℃ from room temperature with the temperature rise rate of 20 ℃/min; And kept 24 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 10, and the germanic acid barium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The 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 by weighing, and ultrasonic agitation 30min in water transfers to after mixing in the autoclave liner of 100mL tetrafluoroethylene; Put it in the stainless steel autoclave,, rise to 200 ℃ from room temperature with the temperature rise rate of 30 ℃/min; And kept 24 hours, naturally cool to room temperature then, with deionized water wash three times; The spinning after drying obtains 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, electrolytic solution and battery assembling are identical with embodiment 10, and the germanic acid barium and the simulated battery test result that prepare in the present embodiment are listed in table 1.
The preparation condition of table 1, earth alkali metal germanate nano material and simulated battery test result
Result according to table 1 can find out that the present invention uses soluble alkaline earth salt and germanium dioxide, can conveniently prepare earth alkali metal germanate nano material through the high pressure water thermal response.As a kind of negative material of novel lithium ion battery, improved the problem of the cycle performance difference that germanium base negative material exists to a great extent, shown higher specific storage.
Claims (10)
1. a method for preparing earth alkali metal germanate nano material comprises the steps:
1) with the aqueous solution and the GeO of alkaline earth salt
2Mixing obtains mixed solution;
2) react after step 1) gained mixed solution is heated up in the teflon-lined reaction kettle, the reaction cooling that finishes obtains said earth alkali metal germanate nano material.
2. method according to claim 1 is characterized in that: said alkaline earth salt is selected from least a in acetate and the oxyhydroxide of following metallic element: Mg, Ca, Sr and Ba.
3. method according to claim 1 and 2 is characterized in that: said alkaline earth salt and GeO
2The ratio of the amount of substance that feeds intake be: 1: 4-10: 1.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: in the said step 3), in the said heating step, temperature rise rate is 5-30 ℃/min; In the said reactions step, temperature is 180 ℃-200 ℃, and the time is 12-48 hour.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: in the said step 3), said teflon-lined volume is 25mL-100mL.
6. the earth alkali metal germanate nano material for preparing of the arbitrary said method of claim 1-5.
7. the described earth alkali metal germanate of claim 6 nano material is characterized in that: said earth alkali metal germanate nano material is at least a in earth alkali metal germanic acid magnesium nano material, earth alkali metal germanic acid calcium nano material, earth alkali metal germanic acid strontium nano material and the earth alkali metal germanic acid barium nano material;
Wherein, in the said earth alkali metal germanic acid magnesium nano material, the apparent physical condition of said germanic acid magnesium is a germanic acid magnesium nanometer sheet, and the diameter of said nanometer sheet is 2-10 μ m, and thickness is 20-80nm;
The apparent physical condition of said germanic acid calcium is a germanic acid calcium one-dimensional nano line, and the length of said germanic acid calcium one-dimensional nano line is 20-1000 μ m, and diameter is 20-70nm;
The apparent physical condition of said germanic acid strontium is a germanic acid strontium one-dimensional nano line, and the length of said germanic acid strontium one-dimensional nano line is 50-1000 μ m, and diameter is 20-80nm;
The apparent physical condition of said germanic acid barium is a germanic acid barium one-dimensional nano line, and the length of said germanic acid barium one-dimensional nano line is 50-500 μ m, and diameter is 20-60nm.
8. claim 6 or 7 said earth alkali metal germanate nano materials are as the application of battery electrode material.
9. the energy storage elements or the portable electric appts that contain claim 6 or 7 said earth alkali metal germanate nano materials.
10. according to Claim 8 or 9 described application, it is characterized in that: said battery electrode material is a lithium ion battery negative material; Said energy storage original paper is a lithium ion battery negative material; Said portable electric appts is mobile telephone, photographic camera, pick up camera, MP3, MP4 or notebook computer.
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