CN106395764B - A kind of preparation method of quaternary lamellar compound - Google Patents
A kind of preparation method of quaternary lamellar compound Download PDFInfo
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- CN106395764B CN106395764B CN201610750756.7A CN201610750756A CN106395764B CN 106395764 B CN106395764 B CN 106395764B CN 201610750756 A CN201610750756 A CN 201610750756A CN 106395764 B CN106395764 B CN 106395764B
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention relates to a kind of preparation methods of quaternary lamellar compound, which solve existing quaternary lamellar compound preparation method it is complicated, higher to equipment requirement the technical issues of, it includes grinding composite molten salt, grinding raw material, configuration reaction solution, last handling process step, the method can be widely used in the preparation field of quaternary lamellar compound.
Description
Technical field
The present invention relates to lithium ion battery electrode material preparation field, and in particular to a kind of preparation side of quaternary lamellar compound
Method.
Background technology
After the industrial revolution, global economy and science and technology are grown rapidly, but always with very while development
More problems.On the one hand, the excessive exploitation of resource causes the drastically reduction of traditional energy.On the other hand, industrial production generates
The timely processing that waste, waste liquid, exhaust gas etc. is unable to causes serious environmental pollution.Therefore, active demand is developed one kind and can be reduced
The burning of fossil fuel and the new technology for recycling low grade thermal energy such as industrial waste heat, vehicle exhaust etc..And thermoelectric power generation skill
Art research and development so that waste heat is converted into electric energy and can be expected to substitution fossil fuel to become to alleviate global climate
Warm problem.The lamellar compound bismuth copper selenolite that intrinsic low-heat a kind of in recent years is led shows good thermoelectricity capability, causes people
Great interest.
Quaternary lamellar compound, such as BiCuSeO, LaCuSeO are typical ZrSiCuAs crystalline structures, generally by carrying
The conductive layer of supplied for electronic transport channel and the layer structure material formed is alternately accumulated as phon scattering region insulation layer.Because of it
With low thermal conductivity, a kind of extremely promising thermoelectric material can be used as.And exciting is above-mentioned quaternary laminarization
Closing object can make ZT values have very big raising by adulterating other elements.
But traditional synthetic method such as solid-phase synthesis, PLD methods, higher to equipment requirement, technological process is generally more multiple
It is miscellaneous, it is difficult to carry out industrialized production.
Invention content
The present invention is exactly to solve existing quaternary lamellar compound preparation method complexity, the technology higher to equipment requirement
Problem, provide a kind of production technology is simplified, can reduce production cost quaternary lamellar compound preparation method.
The present invention includes the following steps：(1) composite molten salt is ground：At room temperature, by two kinds of composite molten salt with molar ratio
For (0.2~1)：It is 5~20 grams that 1 ratio, which weighs total amount, is poured into 10~30min of grinding in mortar, is allowed to be sufficiently mixed；
(2) raw material is ground：By ln compounds, selenium powder, cuprous oxide according to (1~3)：(2~5)：(1~3) molar ratio is weighed, former
The mass ratio for expecting total amount and composite molten salt total amount is (0.05~0.2)：1, grinding uniformly after by composite molten salt pour into again into
Row grinding, makes powder uniform；(3) reaction solution is configured：Reducing agent is weighed, is poured into water heating kettle, water is added in and is allowed to quality percentage
Specific concentration is 5%~20%, is fully dissolved, then material ground in step (2) is poured into water heating kettle and is stirred evenly, by hydro-thermal
Kettle is put into autoclave, and then water heating kettle is put into baking oven；Reaction condition：Oven temperature is 150~250 DEG C, the reaction time
For 24~72h, the volume of water is 25~100mL, the material quality a concentration of 0.02 that step (2) is ground in aqueous solution~
0.05g/mL；(4) last handling process：It takes out autoclave and it is allowed to be cooled to room temperature, it is clear with deionized water and absolute ethyl alcohol respectively
It washes for several times, product is finally collected by the way of centrifugation and is placed in drying the sample synthesized in 50~80 DEG C of drying box.
Preferably, the system of composite molten salt is LiCl-KCl, NaCl-KCl, MgCl2-KCl、Li2SO4-K2SO4、
AlCl3One or more of-NaCl or NaSCN-KSCN.
Preferably, the ln compounds in step (2) are bismuth oxide, bismuth chloride, bismuth nitrate, bismuth citrate, lanthanum nitrate, chlorination
One or more of lanthanum, cerium chloride or cerous nitrate.
Preferably, the reducing agent in step (3) for one kind in polyethylene glycol, polyvinylpyrrolidone or hydrazine hydrate or
It is several.
Electrode is made, and carries out electrochemical property test in the quaternary lamellar compound of the present invention as follows：
Quaternary lamellar compound and conductive black Super-P (10wt%) are sufficiently mixed by mortar grinder mode
It is even, Kynoar (10wt%) and the N-Methyl pyrrolidone of 20 times of Kynoar quality are sequentially added, is sufficiently stirred
Uniformly into paste.Using nickel foam as collector, the above-mentioned material mixed is evenly coated in foam nickel surface, will be made
Pole piece 100 DEG C be dried in vacuo 12 hours, dried pole piece is then subjected to battery assembling in glove box, wherein being electrolysed
Liquid is 1MLiPF6, solvent is that volume ratio is 1：In 1 ethylene carbonate and dimethyl carbonate, battery size 2025.Electrochemistry
Test method is in 0.005~3V voltage ranges, 200mA h g-1Loop test is carried out under constant current conditions.
The present invention has the advantage that：
(1) the quaternary lamellar compound of pure phase is prepared using composite molten salt method, while there is the pattern of comparison rule,
Preparation is simple, controllability is strong, products collection efficiency more than 90%, and under relatively low temperature condition using water heating kettle and
Baking oven can be completed to synthesize so that production cost reduces, application easy to spread, opens the new think of for preparing quaternary lamellar compound
Road.
(2) the invention enables lithium ion battery negative materials more selections, provides and is applied to thermoelectric material
The thinking of lithium ion battery.The layer structure of quaternary lamellar compound is provided for conductive layer and active mass layer, this causes
Material has better electric conductivity, and conductive layer can serve as buffering area, also have certain suppression to the volume expansion of electrode material
It makes and uses, while stratified material has better ion transportation, above advantages cause it to have better electrode material
Application prospect.
Description of the drawings
Fig. 1 is the XRD diagram of BiCuSeO prepared by the embodiment of the present invention 1.
Fig. 2 is BiCuSeO nanometer sheets SEM figures prepared by the embodiment of the present invention 1.
Fig. 3 is charge and discharge cycles curves of the BiCuSeO prepared in inventive embodiments 1 under 200mA/g constant currents.
Specific embodiment
The preparation method with the present invention further retouches the quaternary lamellar compound prepared by the present invention below in conjunction with the accompanying drawings
It states：
Embodiment 1
At room temperature, using molar ratio as LiCl：The ratio of KCl=0.2 weighs the complex salt that total amount is 5 grams, is poured into and grinds
10min is ground in alms bowl, is allowed to be sufficiently mixed.
By bismuth chloride, selenium powder, cuprous oxide according to 3:5:It is 1g that 2 molar ratio, which carries out weighing total amount, will after grinding uniformly
Composite molten salt pours into be ground again, makes powder uniform；
10g polyvinylpyrrolidones are weighed, are poured into water heating kettle, adding in 50mL water makes fully to dissolve, then will be ground
Material, which is poured into water heating kettle, to stir evenly, and water heating kettle is put into autoclave；
Autoclave is put into 200 DEG C of baking oven, reaction time 48h, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the BiCuSeO samples synthesized in 50 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
The stereoscan photograph of product is as shown in Figure 1, the XRD curves of product are as shown in Figure 2.Fig. 3 is that the multiplying power of material is filled
Discharge test figure.As can be seen from Figure 3 as the increase of cycle-index, capacity gradually tend towards stability, illustrate this
Material has preferable cycle performance.
Embodiment 2
At room temperature, the ratio using molar ratio as NaCl-KCl=0.5 weighs the complex salt that total amount is 10 grams, is poured into and grinds
20min is ground in alms bowl, is allowed to be sufficiently mixed.
By bismuth chloride, selenium powder, cuprous oxide according to 2:2:It is 1g that 1 molar ratio, which carries out weighing total amount, will after grinding uniformly
Composite molten salt pours into be ground again, makes powder uniform；
1g polyvinylpyrrolidones are weighed, are poured into water heating kettle, adding in 20mL water makes fully to dissolve, then by ground material
It pours into water heating kettle and stirs evenly, water heating kettle is put into autoclave；
Autoclave is put into 150 DEG C of baking oven, the reaction time for 24 hours, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the BiCuSeO samples synthesized in 70 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Embodiment 3
At room temperature, using molar ratio as LiNO3-KNO3=1 ratio weighs the complex salt that total amount is 20 grams, is poured into and grinds
20min is ground in alms bowl, is allowed to be sufficiently mixed.
By bismuth oxide, selenium powder, cuprous oxide according to 1:2:It is 1g that 1 molar ratio, which carries out weighing total amount, will after grinding uniformly
Composite molten salt pours into be ground again, makes powder uniform；
1gPVP is weighed, is poured into water heating kettle, adding in 20mL water makes fully to dissolve, then ground material is poured into water heating kettle
In stir evenly, water heating kettle is put into autoclave；
Autoclave is put into 200 DEG C of baking oven, reaction time 48h, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the BiCuSeO samples synthesized in 80 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Embodiment 4
At room temperature, using molar ratio as LiNO3-KNO3=0.5 ratio weighs the complex salt that total amount is 20 grams, is poured into
20min is ground in mortar, is allowed to be sufficiently mixed.
By bismuth nitrate, selenium powder, cuprous oxide according to 2:2:It is 1.5g that 3 molar ratio, which carries out weighing total amount, after grinding uniformly
Composite molten salt is poured into and is ground again, makes powder uniform；
3.8g hydrazine hydrates are weighed, are poured into water heating kettle, adding in 38mL water makes fully to dissolve, then ground material is poured into water
It is stirred evenly in hot kettle, water heating kettle is put into autoclave；
Autoclave is put into 250 DEG C of baking oven, reaction time 72h, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the BiCuSeO samples synthesized in 80 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Embodiment 5
At room temperature, using molar ratio as LiNO3-KNO3=1 ratio weighs the complex salt that total amount is 15 grams, is poured into and grinds
20min is ground in alms bowl, is allowed to be sufficiently mixed.
By bismuth nitrate, selenium powder, cuprous oxide according to 2:2:It is 1.5g that 1 molar ratio, which carries out weighing total amount, after grinding uniformly
Composite molten salt is poured into and is ground again, makes powder uniform；
3.8g hydrazine hydrates are weighed, are poured into water heating kettle, adding in 38mL water makes fully to dissolve, then ground material is poured into water
It is stirred evenly in hot kettle, water heating kettle is put into autoclave；
Autoclave is put into 240 DEG C of baking oven, reaction time 72h, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the BiCuSeO samples synthesized in 80 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Embodiment 6
At room temperature, using molar ratio as LiCl：The ratio of KCl=0.2 weighs the complex salt that total amount is 20 grams, is poured into and grinds
20min is ground in alms bowl, is allowed to be sufficiently mixed.
By bismuth oxide, selenium powder, cuprous oxide according to 1:2:It is 2g that 1 molar ratio, which carries out weighing total amount, will after grinding uniformly
Composite molten salt pours into be ground again, makes powder uniform；
5g polyethylene glycol is weighed, is poured into water heating kettle, adding in 100mL water makes fully to dissolve, then ground material is poured into
It is stirred evenly in water heating kettle, water heating kettle is put into autoclave；
Autoclave is put into 200 DEG C of baking oven, reaction time 48h, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the BiCuSeO samples synthesized in 50 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Embodiment 7
At room temperature, using molar ratio as LiCl：The ratio of KCl=0.2 weighs the complex salt that total amount is 20 grams, is poured into and grinds
20min is ground in alms bowl, is allowed to be sufficiently mixed.
By lanthanum chloride, selenium powder, cuprous oxide according to 1:2:It is 2g that 1 molar ratio, which carries out weighing total amount, will after grinding uniformly
Composite molten salt pours into be ground again, makes powder uniform；
5g polyethylene glycol is weighed, is poured into water heating kettle, adding in 100mL water makes fully to dissolve, then ground material is poured into
It is stirred evenly in water heating kettle, water heating kettle is put into autoclave；
Autoclave is put into 200 DEG C of baking oven, reaction time 48h, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the LaCuSeO samples synthesized in 50 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Embodiment 8
At room temperature, the ratio using molar ratio as NaCl-KCl=0.5 weighs the complex salt that total amount is 10 grams, is poured into and grinds
20min is ground in alms bowl, is allowed to be sufficiently mixed.
By cerium chloride, selenium powder, cuprous oxide according to 2:2:It is 1g that 1 molar ratio, which carries out weighing total amount, will after grinding uniformly
Composite molten salt pours into be ground again, makes powder uniform；
1g polyvinylpyrrolidones are weighed, are poured into water heating kettle, adding in 20mL water makes fully to dissolve, then by ground material
It pours into water heating kettle and stirs evenly, water heating kettle is put into autoclave；
Autoclave is put into 150 DEG C of baking oven, the reaction time for 24 hours, baking oven is closed after the reaction time reaches.
It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol for several times, finally use
The mode of centrifugation collects product and is placed in drying the CeCuSeO samples synthesized in 70 DEG C of drying box.Simultaneously by material system
Electro-chemical test is carried out into battery electrode.
Electro-chemical test part is with embodiment 1, the prepared materials show experiment knot almost the same with embodiment 1
Fruit.
Claims (4)
1. a kind of preparation method of quaternary lamellar compound, it is characterized in that including the following steps：
(1) composite molten salt is ground：At room temperature, by two kinds of composite molten salt using molar ratio as (0.2~1)：1 ratio weighs total
It is 5~20 grams to measure, and is poured into 10~30min of grinding in mortar, is allowed to be sufficiently mixed；
(2) raw material is ground：By ln compounds, selenium powder, cuprous oxide according to (1~3)：(2~5)：(1~3) molar ratio is claimed
The mass ratio of amount, raw material total amount and composite molten salt total amount is (0.05~0.2)：1, composite molten salt is poured into after grinding uniformly
It is ground again, makes powder uniform；
(3) reaction solution is configured：Weigh reducing agent, pour into water heating kettle, add in water be allowed to mass percent concentration for 5%~
20%, it fully dissolves, then material ground in step (2) is poured into water heating kettle and is stirred evenly, water heating kettle is put into autoclave
In, then water heating kettle is put into baking oven；Reaction condition：Oven temperature be 150~250 DEG C, the reaction time be 24~72h, water
Volume for 25~100mL, step (2) is ground in aqueous solution a concentration of 0.02~0.05g/mL of material quality；
(4) last handling process：It takes out autoclave and it is allowed to be cooled to room temperature, respectively with deionized water and washes of absolute alcohol number
It is secondary, product is finally collected by the way of centrifugation and is placed in drying the sample synthesized in 50~80 DEG C of drying box.
2. the preparation method of quaternary lamellar compound according to claim 1, it is characterised in that the composite molten salt
System is LiCl-KCl, NaCl-KCl, MgCl2-KCl、Li2SO4-K2SO4、AlCl3One kind in-NaCl or NaSCN-KSCN
It is or several.
3. the preparation method of quaternary lamellar compound according to claim 1, which is characterized in that in the step (2)
Ln compounds are one in bismuth oxide, bismuth chloride, bismuth nitrate, bismuth citrate, lanthanum nitrate, lanthanum chloride, cerium chloride or cerous nitrate
Kind is several.
4. the preparation method of quaternary lamellar compound according to claim 1, which is characterized in that in the step (3)
Reducing agent one or more of for polyethylene glycol, polyvinylpyrrolidone or hydrazine hydrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643085A (en) * | 2012-04-13 | 2012-08-22 | 清华大学 | Bi Cu 1-x SeO-based oxide thermoelectric ceramic material and preparation method thereof |
| CN102655204A (en) * | 2012-04-28 | 2012-09-05 | 北京航空航天大学 | Sr-doping oxide BiCuSeO thermoelectric material and preparation method thereof |
| CN103011838A (en) * | 2012-10-24 | 2013-04-03 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of BiCuSeO-based pyroelectric oxide powder |
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2016
- 2016-08-29 CN CN201610750756.7A patent/CN106395764B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643085A (en) * | 2012-04-13 | 2012-08-22 | 清华大学 | Bi Cu 1-x SeO-based oxide thermoelectric ceramic material and preparation method thereof |
| CN102655204A (en) * | 2012-04-28 | 2012-09-05 | 北京航空航天大学 | Sr-doping oxide BiCuSeO thermoelectric material and preparation method thereof |
| CN103011838A (en) * | 2012-10-24 | 2013-04-03 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of BiCuSeO-based pyroelectric oxide powder |
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