CN104157864A - Preparation method of lithium-ion perfluorinated sulfonic acid resin cladding aluminum-lithium alloy material - Google Patents
Preparation method of lithium-ion perfluorinated sulfonic acid resin cladding aluminum-lithium alloy material Download PDFInfo
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- CN104157864A CN104157864A CN201410333524.2A CN201410333524A CN104157864A CN 104157864 A CN104157864 A CN 104157864A CN 201410333524 A CN201410333524 A CN 201410333524A CN 104157864 A CN104157864 A CN 104157864A
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Abstract
The invention relates to the technical field of a lithium ion battery, and aims at providing a preparation method of a lithium-ion perfluorinated sulfonic acid resin cladding aluminum-lithium alloy material. The preparation method comprises the following steps: preparing a tetrahydrofuran solution of lithium aluminum hydride, preparing a macroporous carbon material, adding the macroporous carbon material to the tetrahydrofuran solution of the lithium aluminum hydride to prepare a macroporous carbon supported lithium aluminum hydride composite material and further to obtain a macroporous carbon supported aluminum-lithium composite material; preparing a Li<+> perfluorinated sulfonic acid resin solution, and preparing the macroporous carbon supported Li<+> perfluorinated sulfonic acid resin cladding aluminum-lithium alloy composite material by virtue of the Li<+> perfluorinated sulfonic acid resin solution and the macroporous carbon supported aluminum-lithium composite material. The prepared lithium-ion perfluorinated sulfonic acid resin cladding aluminum-lithium alloy material has the advantages that organic electrolyte is safer when being applied to the battery; the electrode reaction reversibility is good; the chemical stability and thermal stability are good; the price is low, and easiness in preparation can be realized; no pollution is caused; safety of the lithium ion battery can be improved by virtue of oxidation resistance.
Description
Technical field
The invention relates to technical field of lithium ion, particularly the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material.
Background technology
The advantages such as that lithium ion battery has is lightweight, capacity large, memory-less effect, thereby obtained generally application.Present many digital equipments have all adopted lithium ion battery to make power supply.The energy density of lithium ion battery is very high, and its capacity is 1.5～2 times of Ni-MH battery of same weight, and there is very low self-discharge rate, be not the major reason of its extensive use containing advantages such as noxious substances.The people such as nineteen ninety Japan Nagoura are developed into taking petroleum coke as negative pole, with LiCoO
2lithium ion battery for anodal: LiC
6| LiClO
4-PC+EC|LiCoO
2.The same year.Moli and the large Battery Company of Sony two are declared the lithium ion battery of releasing taking carbon as negative pole.1991, Sony energy technology company and battery portion developed jointly a kind of lithium ion battery taking glycan alcohol RESEARCH OF PYROCARBON (PFA) as negative pole.
Lithium ion battery negative material has graphite (C
6), sulfide: TiS
2, NbS
2, oxide: WO
3, V
2o
5, SnO
2deng.Taking graphite cathode material as example, negative reaction in charge and discharge process: C
6+ xLi
++ xe==Li
xc
6, theoretical capacity is 372mAh g
-1(LiC
6).In the time that battery is charged, on the positive pole of battery, there is lithium ion to generate, the lithium ion of generation arrives negative pole through electrolyte movement.And be layer structure as the graphite of negative pole, and it has a lot of micropores, and the lithium ion that arrives negative pole is just embedded in the micropore of carbon-coating, forms lithium intercalation compound (Li
xc
6), the lithium ion of embedding is more, and charging capacity is higher.In the time that battery is discharged, the lithium ion being embedded in graphite linings is deviate from, and positive pole is got back in motion again.Get back to anodal lithium ion more, discharge capacity is higher.
Must be to possess following requirement as the negative material of lithium battery: (1) lithium storage capacity is high; (2) embedding, the deintercalation reaction of lithium in negative material is fast, and the diffusion coefficient of lithium ion in solid phase is large, little in the mobile impedance at electrode-electric solution liquid interface; (3) existence of lithium ion in electrode material is stable; (4), in the charge and discharge cycles of battery, negative material change in volume is little; (5) electron conduction is high; (6) negative material does not dissolve in electrolyte.
Metallic aluminium can form up to Li with Li
9al
4alloy, contrast Li
4.4sn (994mAh g
-1) there is very high theoretical specific capacity (2234mAh g
-1), far above traditional graphite cathode material.Lithium ion embed and the process of deviating from, the electric discharge of aluminium negative pole and charging curve respectively 0.2 and 0.45V left and right present stable embedding, de-lithium platform.Therefore, alumina-base material is a kind of very promising lithium ion battery negative material.At present, the subject matter that metallic aluminium negative material faces is: in charge and discharge cycles process, with Li-Sn alloy phase ratio, the reversible generation of Li-Al alloy is accompanied by larger change in volume with decomposition, causes alloy more easily to produce crack and efflorescence, and contact resistance is increased, form irreversible capacity loss, even lose reversible lithium storage effect, finally cause electrode failure, therefore the simple cycle performance of lithium ion battery taking aluminium as negative material is very poor.
Even if aluminum particulate can be coated by copper or carbon, alleviated to a certain extent the active material that the efflorescence of aluminium in removal lithium embedded process causes and run off, but its volumetric expansion must cause cracking and the destruction of coated copper film or carbon film.Therefore the negative pole that, the coated volumetric expansion that can not thoroughly solve metallic aluminium aluminium in removal lithium embedded process of simple copper clad or carbon causes destroys.Must be coated in the mode of aluminium lithium alloy, just likely eliminate the volumetric expansion of aluminium in removal lithium embedded process to the destruction of carrier material.But aluminium lithium alloy is quite active, be difficult to by conventional technological means, aluminium lithium alloy particle is coated.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, and a kind of Li is provided
+type perfluorinated sulfonic resin metallized aluminum lithium alloy, and the preparation method of lithium ion battery negative material taking macropore carbon as carrier.For solving the problems of the technologies described above, solution of the present invention is:
The preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material is provided, and Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material is for the negative material as lithium battery, and described preparation method specifically comprises the steps:
(1) in the glove box of argon gas atmosphere, get aluminium powder and lithium sheet and be placed in reactor (reactors of 316 stainless steels), after sealed reactor, shift out glove box, hydrogenation plant is accessed to reactor, for passing into hydrogen to reactor and reactor being vacuumized; Wherein, the mass ratio of aluminium powder and lithium sheet is 27:7;
(2) reactor is vacuumized, vacuum degree reaches 10
2after Pascal, the temperature of reactor is risen to 550 DEG C, react and within 2 hours, generate block lithium-aluminium alloy; After reaction finishes, reactor is cooled to 200 DEG C, and in reactor, passes into 40 atmospheric High Purity Hydrogen (purity: 99.999%) by hydrogenation plant, react after 5 hours, cool the temperature to again 20 DEG C, the hydrogen in reactor is discharged, obtain Lithium Aluminium Hydride;
(3) to being equipped with in the reactor (reactors of 316 stainless steels) of Lithium Aluminium Hydride, add oxolane liquid, stirring and dissolving obtains the tetrahydrofuran solution of Lithium Aluminium Hydride, and the concentration that makes Lithium Aluminium Hydride in solution is 2.5wt%～15wt%;
(4) take hydrophilic nano CaCO
3and glucose, be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix 30 minutes, make glucose dissolve and with nanometer CaCO
3be uniformly dispersed, heating evaporates the water, and then at 160 DEG C, solidifies 6 hours, obtains cured product; Again cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours, obtains carbonized product and is cooled to 20 DEG C; Carbonized product is washed with hydrochloric acid and the deionized water of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C;
Wherein, hydrophilic nano CaCO
3with the mass ratio of water soluble starch be 1: 1, and hydrophilic nano CaCO
3addition be that the addition of 10g and glucose is 10g;
(5) get the tetrahydrofuran solution that the macropore material with carbon element making in step (4) adds the Lithium Aluminium Hydride obtaining in step (3), ultrasonic (supersonic frequency 40kHz) mixes after 30min, evaporate oxolane, obtain the carbon-supported Lithium Aluminium Hydride composite material of macropore;
(6) carbon-supported the macropore making in step (5) Lithium Aluminium Hydride composite material is placed in to reactor (reactors of 316 stainless steels), at 400 DEG C, vacuumize after 4 hours, obtain the carbon-supported aluminium lithium composite of macropore material, and carbon-supported macropore aluminium lithium composite material is cooled to 20 DEG C;
(7) get perfluorinated sulfonic resin 10g (originating from E.I.Du Pont Company) and be placed in the 100mL LiOH aqueous solution, at 80 DEG C, stir after 2 hours, filter and obtain product; Take out product and with after washed with de-ionized water, carry out vacuumize, obtain Li
+type perfluorinated sulfonic resin;
Get again the Li that 10g makes
+type perfluorinated sulfonic resin is dissolved in 200mL 1-METHYLPYRROLIDONE (NMP), obtains Li
+type perfluor sulfoacid resin solution;
(8), in the glove box of argon gas atmosphere, get the Li making in step (7)
+type perfluor sulfoacid resin solution is added in the carbon-supported aluminium lithium composite of the macropore material making in step (6), after stirring at 150 DEG C evaporate to dryness, obtain the carbon-supported Li of macropore
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites;
Wherein, Li
+the addition of type perfluor sulfoacid resin solution is 50～200mL, and the addition of the carbon-supported aluminium lithium composite of macropore material is 1g.
As further improvement, in the glove box of described argon gas atmosphere, water content and oxygen content are all less than 1ppm.
As further improvement, the perfluorinated sulfonic resin in described step (7) adopts film or pulverous perfluorinated sulfonic resin.
As further improvement, the LiOH aqueous solution in described step (7) is that mass concentration is the LiOH aqueous solution of 10wt%.
As further improvement, described hydrophilic nano CaCO
3particle diameter be 15～40nm.
As further improvement, the hydrogenation plant in described step (1), comprises pressure-reducing valve, high-purity High Pressure Hydrogen bottle, hydrogen storehouse, Pressure gauge, unidirectional stop valve, vacuum pump, pipeline docking adapter, vacuum meter;
High-purity High Pressure Hydrogen bottle (1-1), pressure-reducing valve (1-6), hydrogen storehouse (1-3), unidirectional stop valve (1-10) connect successively, are connected with Pressure gauge (1-11) on hydrogen storehouse (1-3); Between hydrogen storehouse (1-3) and unidirectional stop valve (1-10), be connected with unidirectional stop valve (1-9), unidirectional stop valve (1-9) is connected with vacuum pump (1-4), between unidirectional stop valve (1-9) and vacuum pump (1-4), is also connected with vacuum meter (1-12); Hydrogen storehouse (1-3) is also connected with unidirectional stop valve (1-8), and unidirectional stop valve (1-8) is connected with pipeline docking adapter (1-5);
Reactor is connected with unidirectional stop valve (1-7), and is connected with the pipeline docking adapter (1-5) in hydrogenation plant by unidirectional stop valve (1-7).
As further improvement, the intensification of described reactor is heated by reactor is arranged in electric furnace, utilizes the heating of electric furnace to realize.
Operation principle of the present invention:
In step (2), aluminium and lithium generate block lithium-aluminium alloy 550 DEG C of reactions after 2 hours.Because aluminium lithium alloy is extremely active, in air, there is spontaneous combustion blast, be therefore difficult to direct use.Aluminium lithium alloy is cooled to 200 DEG C and generates Lithium Aluminium Hydride after passing into 40 atmospheric High Purity Hydrogen.Lithium Aluminium Hydride is stable in dry air, can be dissolved in oxolane.
In step (5), in evaporate to dryness process, Lithium Aluminium Hydride in macropore material with carbon element endoporus crystallization and filling in macropore carbon endoporus.
In step (6), while vacuumizing at 400 DEG C, Lithium Aluminium Hydride is put hydrogen by stage:
3LiAlH
4→Li
3AlH
6+2Al+3H
2
2Li
3AlH
6→6LiH+2Al+3H
2
2LiH+2Al→2LiAl+H
2
After 4 hours, put hydrogen and finish, particle size dwindles, and between lithium-aluminium alloy particle and macropore carbon inwall, leaves space, and the volumetric expansion that in available buffer lithium cell charging process, lithium-aluminium alloy particle embedding lithium produces, avoids the destruction to macropore material with carbon element.
In step (8), evaporate to dryness process makes Li at 150 DEG C
+type perfluorinated sulfonic resin solidifies at aluminium lithium alloy particle surface, forms coating layer, makes aluminium lithium alloy and air isolated, also can suppress aluminium lithium alloy and react with electrolyte, the conduction of lithium ion while but not affecting aluminium lithium alloy particle removal lithium embedded.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention utilizes aluminium to have the characteristic of high storage lithium specific capacity, forms a kind of lithium ion battery negative material of high power capacity; Lithium Aluminium Hydride tetrahydrofuran solution is conducive to Lithium Aluminium Hydride to be filled to equably in the mesoporous and macropore of macropore material with carbon element, is conducive to form the carbon-supported Li of macropore that aluminium lithium alloy is evenly distributed
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites; Li
+type perfluorinated sulfonic resin coating layer completely cuts off aluminium lithium alloy and air, the fail safe that greatly improves this negative material.
The carbon-supported Li of macropore prepared by the present invention
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites, has: (1) stably charging/discharging voltage platform makes organic bath safer in battery applications; (2) good electrode reaction invertibity; (3) good chemical stability and thermal stability; (4) cheap and be easy to preparation; (5) pollution-free; (6) fail safe of anti-oxidant raising lithium ion battery.
Brief description of the drawings
Fig. 1 is the device schematic diagram of preparing Lithium Aluminium Hydride in embodiment 1.
Fig. 2 is lithium ion battery charging and discharging curve schematic diagram prepared by embodiment nine.
Reference numeral in figure is: the high-purity High Pressure Hydrogen bottle of 1-1; 1-2 reactor; 1-3 hydrogen storehouse; 1-4 vacuum pump; 1-5 pipeline docking adapter; 1-6 pressure-reducing valve; 1-7 unidirectional stop valve; 1-8 unidirectional stop valve; 1-9 unidirectional stop valve; 1-10 unidirectional stop valve; 1-11 Pressure gauge; 1-12 vacuum meter; 1-13 electric furnace; 2-1 charging curve; 2-2 discharge curve.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
The preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material, Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material is for the negative material as lithium battery, and described preparation method specifically comprises the steps:
(1) be all less than in the glove box of argon gas atmosphere of 1ppm at water content and oxygen content, get aluminium powder and lithium sheet and be placed in the reactor 1-2 of 316 stainless steels, after sealed reactor 1-2, shift out glove box, access hydrogenation plant; Wherein, the mass ratio of aluminium powder and lithium sheet is 27:7;
(2) reactor 1-2 is vacuumized, vacuum degree reaches 10
2after Pascal, the temperature of reactor 1-2 is risen to 550 DEG C, react and within 2 hours, generate block lithium-aluminium alloy; After reaction finishes, reactor 1-2 is cooled to 200 DEG C, and passes into 40 atmospheric High Purity Hydrogen (purity: 99.999%), react 5 hours in reactor 1-2; Temperature is down to 20 DEG C, and the hydrogen in reactor 1-2 is discharged, and obtains Lithium Aluminium Hydride;
(3) in the reactor 1-2 of 316 stainless steels containing Lithium Aluminium Hydride, add oxolane liquid, stirring and dissolving obtains the tetrahydrofuran solution of Lithium Aluminium Hydride; Wherein the concentration of Lithium Aluminium Hydride is determined by the addition of oxolane; The concentration of Lithium Aluminium Hydride is 2.5wt%～15wt%;
(4) take in mass ratio the nanometer CaCO that commercially available particle diameter is 15～40nm at 1: 1
3(10g) and glucose (10g), be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make glucose dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 20 DEG C.Product washs with hydrochloric acid and the deionized water of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C.
(5) get the macropore material with carbon element making in step (4) and add the Lithium Aluminium Hydride tetrahydrofuran solution obtaining in step (3), ultrasonic (supersonic frequency 40kHz) mixes after 30min, evaporate oxolane, obtain the carbon-supported Lithium Aluminium Hydride composite material of macropore;
(6) carbon-supported the macropore making in step (5) Lithium Aluminium Hydride composite material is placed in to the reactor 1-2 of 316 stainless steels, at 400 DEG C, vacuumizes after 4 hours, obtain the carbon-supported aluminium lithium composite of macropore material, be cooled to 20 DEG C;
(7) get film or pulverous perfluorinated sulfonic resin 10g (originating from E.I.Du Pont Company) and be placed in the LiOH aqueous solution of 100mL10wt%, at 80 DEG C, stir after 2 hours, filter and obtain product; Take out product and with after washed with de-ionized water, carry out vacuumize, obtain Li
+type perfluorinated sulfonic resin;
Again by the Li making
+type perfluorinated sulfonic resin is dissolved in 200mL 1-METHYLPYRROLIDONE (NMP), obtains Li
+type perfluor sulfoacid resin solution;
(8) be all less than in the glove box of argon gas atmosphere of 1ppm at water content and oxygen content, get the Li making in step (7)
+type perfluor sulfoacid resin solution is added in the carbon-supported aluminium lithium composite of the macropore material making in step (6), and evaporate to dryness after stirring, obtains the carbon-supported Li of macropore
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites;
Wherein, Li
+the addition of type perfluor sulfoacid resin solution is 50～200mL, and the addition of the carbon-supported aluminium lithium composite of macropore material is 1g.
Hydrogenation plant wherein comprises pressure-reducing valve, high-purity High Pressure Hydrogen bottle, hydrogen storehouse, Pressure gauge, unidirectional stop valve, vacuum pump, pipeline docking adapter, vacuum meter.High-purity High Pressure Hydrogen bottle 1-1, pressure-reducing valve 1-6, hydrogen storehouse 1-3, unidirectional stop valve 1-10 connect successively, on the 1-3 of hydrogen storehouse, are connected with Pressure gauge 1-11; Between hydrogen storehouse 1-3 and unidirectional stop valve 1-10, be connected with unidirectional stop valve 1-9, unidirectional stop valve 1-9 is connected with vacuum pump 1-4, between unidirectional stop valve 1-9 and vacuum pump 1-4, is also connected with vacuum meter 1-12; Hydrogen storehouse 1-3 is also connected with unidirectional stop valve 1-8, and unidirectional stop valve 1-8 and pipeline docking adapter 1-5 coupled reaction device 1-2 are connected with unidirectional stop valve 1-7, and is connected with the pipeline docking adapter 1-5 in hydrogenation plant by unidirectional stop valve 1-7.
In addition, the intensification of reactor 1-2 is heated by being arranged in electric furnace 1-13, utilizes the heating of electric furnace 1-13 to realize
The following examples can make this professional professional and technical personnel's comprehend the present invention, but do not limit the present invention in any way.
Embodiment 1 Lithium Aluminium Hydride preparation
In the glove box of argon atmospher protection (water content and oxygen content are all less than 1ppm); get aluminium powder 27g; lithium sheet 7g is placed in the reactor of 316 stainless steels; after sealed reactor, shift out glove box; by pipeline docking adapter 1-5 access hydrogenation plant; as shown in Figure 1, all valves of hydrogenation plant are initial all in closed condition.Open break valve 1-7,1-8,1-9, be evacuated to vacuum meter 1-12 and show 10
2after Pascal, close break valve 1-9.Electric furnace 1-13 is warming up to 550 DEG C, when temperature of reactor rose to 550 DEG C of reactions after 2 hours, is cooled to 200 DEG C; Open pressure-reducing valve 1-6 and make the High Purity Hydrogen (purity: 99.999%) be filled with hydrogen storehouse 1-3, make the pressure of hydrogen in reactor 1-3 maintain 40 atmospheric pressure, hydrogen pressure is shown by Pressure gauge 1-11 in high-purity High Pressure Hydrogen bottle 1-1; Open break valve 1-7 and 1-8, make High Purity Hydrogen enter reactor; React after 5 hours, close pressure-reducing valve 1-6, open break valve 1-10 and put hydrogen, discharge after the hydrogen in reactor, close break valve 1-10, furnace temperature is down to 20 DEG C and obtains Lithium Aluminium Hydride.
Embodiment 2 Lithium Aluminium Hydride tetrahydrofuran solution preparations
In the glove box of argon atmospher protection (water content and oxygen content are all less than 1ppm); get aluminium powder 2.7g; lithium sheet 0.7g is placed in the reactor of 316 stainless steels; after sealed reactor, shift out glove box; by pipeline docking adapter 1-5 access hydrogenation plant; as shown in Figure 1, all valves of hydrogenation plant are initial all in closed condition.Open break valve 1-7,1-8,1-9, be evacuated to vacuum meter 1-12 and show 10
2after Pascal, close break valve 1-9.Electric furnace 1-13 is warming up to 550 DEG C, when temperature of reactor rose to 550 DEG C of reactions after 2 hours, is cooled to 200 DEG C; Open pressure-reducing valve 1-6 and make the High Purity Hydrogen (purity: 99.999%) be filled with hydrogen storehouse 1-3, make the pressure of hydrogen in reactor 1-3 maintain 40 atmospheric pressure, hydrogen pressure is shown by Pressure gauge 1-11 in high-purity High Pressure Hydrogen bottle 1-1; Open break valve 1-7 and 1-8, make High Purity Hydrogen enter reactor; React after 5 hours, close pressure-reducing valve 1-6, open break valve 1-10 and put hydrogen, discharge after the hydrogen in reactor, close break valve 1-10, furnace temperature is down to 20 DEG C, open break valve 1-9 and pump remaining hydrogen in reactor, close break valve 1-9, open reactor, add 75mL oxolane, stirring and dissolving obtains the tetrahydrofuran solution containing 5.3wt% Lithium Aluminium Hydride.
Open after reactor, if the 26.5mL oxolane only adding, stirring and dissolving is by the tetrahydrofuran solution obtaining containing 15wt% Lithium Aluminium Hydride; But the oxolane adding reaches 159mL, stirring and dissolving is by the tetrahydrofuran solution obtaining containing 2.5wt% Lithium Aluminium Hydride.
Embodiment 3 macropore material with carbon element preparations
Particle diameter is the nanometer CaCO of 15～40nm
310g and glucose 10g, be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make glucose dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 20 DEG C.Product washs with hydrochloric acid and the deionized water of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C.
The carbon-supported Lithium Aluminium Hydride composite material preparation of embodiment 4 macropore
In the glove box of argon atmospher protection (water content and oxygen content are all less than 1ppm); get aluminium powder 27g; lithium sheet 7g is placed in the reactor of 316 stainless steels; after sealed reactor, shift out glove box; by pipeline docking adapter 1-5 access hydrogenation plant; as shown in Figure 1, all valves of hydrogenation plant are initial all in closed condition.Open break valve 1-7,1-8,1-9, be evacuated to vacuum meter 1-12 and show 10
2after Pascal, close break valve 1-9.Electric furnace 1-13 is warming up to 550 DEG C, when temperature of reactor rose to 550 DEG C of reactions after 2 hours, is cooled to 200 DEG C; Open pressure-reducing valve 1-6 and make the High Purity Hydrogen (purity: 99.999%) be filled with hydrogen storehouse 1-3, make the pressure of hydrogen in reactor 1-3 maintain 40 atmospheric pressure, hydrogen pressure is shown by Pressure gauge 1-11 in high-purity High Pressure Hydrogen bottle 1-1; Open break valve 1-7 and 1-8, make High Purity Hydrogen enter reactor; React after 5 hours, close pressure-reducing valve 1-6, open break valve 1-10 and put hydrogen, discharge after the hydrogen in reactor, close break valve 1-10, furnace temperature is down to 20 DEG C, open break valve 1-9 and pump remaining hydrogen in reactor, close break valve 1-9, open reactor, add 375mL oxolane, stirring and dissolving obtains the tetrahydrofuran solution containing 10.1wt% Lithium Aluminium Hydride.
The macropore carbon 10g getting in embodiment tri-adds the above Lithium Aluminium Hydride tetrahydrofuran solution 100mL obtaining, ultrasonic (supersonic frequency 40kHz) evaporates oxolane after mixing 30min, obtains the carbon-supported Lithium Aluminium Hydride composite material of macropore containing 47.6wt% Lithium Aluminium Hydride content.
The carbon-supported Al-Li Alloy Matrix Composites preparation of embodiment 5 macropore
Get the carbon-supported Lithium Aluminium Hydride composite material of the macropore obtaining in embodiment tetra-, be placed in the reactor of 316 stainless steels, at 400 DEG C, vacuumize after 4 hours, be cooled to 20 DEG C and obtain the carbon-supported Al-Li Alloy Matrix Composites of macropore.
Embodiment 6Li
+the preparation of type perfluor sulfoacid resin solution
City dealer's perfluorinated sulfonic resin film 10g (originating from E.I.Du Pont Company) is placed in to the 100mL LiOH aqueous solution (10wt%), and 80 DEG C are stirred filtration after 2 hours, take out with carrying out vacuumize after washed with de-ionized water, obtain Li
+type perfluorinated sulfonic resin; Be dissolved in 200mL 1-METHYLPYRROLIDONE (NMP), obtained the Li that concentration is 4.76wt%
+type perfluor sulfoacid resin solution.
The carbon-supported Li of embodiment 7 macropore
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites
In the glove box of argon atmospher protection (water content and oxygen content are all less than 1ppm), the carbon-supported aluminium lithium composite of the macropore material (1g) obtaining by embodiment tetra-, five is added into the 50mL Li that embodiment six obtains
+in type perfluor sulfoacid resin solution, evaporate to dryness after stirring, obtains the carbon-supported Li of macropore
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites.
Embodiment 8 is with the carbon-supported Li of macropore
+the negative pole preparation of type perfluorinated sulfonic resin metallized aluminum lithium alloy
In the glove box of argon atmospher protection (water content and oxygen content are all less than 1ppm), the carbon-supported aluminium lithium composite of the macropore material (1g) obtaining by embodiment tetra-, five is added into the 100mL Li that embodiment six obtains
+in type perfluor sulfoacid resin solution, the evaporate to dryness at latter 150 DEG C that stirs, obtains the carbon-supported Li of macropore
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites.
By above-mentioned negative material: Li
+type perfluorinated sulfonic resin: acetylene black is 80: 10: 10 in mass ratio, mechanical mixture 30 minutes adds NMP to be modulated into paste in right amount, is coated on copper film, dries in the shade; At 100Kg cm
-2pressure under compressing, obtain negative pole.
Embodiment 9 is with the carbon-supported Li of macropore
+the lithium battery that type perfluorinated sulfonic resin metallized aluminum lithium alloy is negative material
In the glove box of argon atmospher protection (water content and oxygen content are all less than 1ppm), the carbon-supported aluminium lithium composite of the macropore material (1g) obtaining by embodiment tetra-, five is added into the 200mL Li that embodiment six obtains
+in type perfluor sulfoacid resin solution, the evaporate to dryness at latter 150 DEG C that stirs, obtains the carbon-supported Li of macropore
+type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites.
By above-mentioned negative material: Li
+type perfluorinated sulfonic resin: acetylene black is 80: 10: 10 in mass ratio, mechanical mixture 30 minutes adds NMP to be modulated into paste in right amount, is coated on copper film, and the final vacuum that dries in the shade is dry; At 100Kg cm
-2pressure under compressing, obtain negative pole.
By anode material for lithium-ion batteries nano-TiO
2: Li
+type perfluorinated sulfonic resin: acetylene black is 80: 10: 10 in mass ratio, mechanical mixture 30 minutes adds NMP to be modulated into paste in right amount, is modulated into paste, is coated on aluminium film, and the final vacuum that dries in the shade is dry; At 100Kg cm
-2pressure under compressing, obtain TiO
2anodal.
Taking microporous polypropylene membrane as barrier film, the electrode material side of above-mentioned positive pole and negative pole forms sandwich structure, built-in electrolyte with barrier film in opposite directions; Electrolyte is with LiPF
6for solute, ethylene carbonate is solvent, contains 151.9 grams of lithium hexafluoro phosphates in one liter of electrolyte.Fig. 2 is the charging and discharging curve of assembled battery.The electric weight that abscissa unit discharges for every gram of aluminium.Charge-discharge magnification: 0.2C, temperature: 25 DEG C.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have a lot of distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (7)
- The preparation method of 1.Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material, Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material is used for the negative material as lithium battery, it is characterized in that, and described preparation method specifically comprises the steps:(1) in the glove box of argon gas atmosphere, get aluminium powder and lithium sheet is placed in reactor, after sealed reactor, shift out glove box, hydrogenation plant is accessed to reactor, for passing into hydrogen to reactor and reactor being vacuumized; Wherein, the mass ratio of aluminium powder and lithium sheet is 27:7;(2) reactor is vacuumized, vacuum degree reaches 10 2after Pascal, the temperature of reactor is risen to 550 DEG C, react and within 2 hours, generate block lithium-aluminium alloy; After reaction finishes, reactor is cooled to 200 DEG C, and in reactor, passes into 40 atmospheric High Purity Hydrogen (purity: 99.999%) by hydrogenation plant, react after 5 hours, cool the temperature to again 20 DEG C, the hydrogen in reactor is discharged, obtain Lithium Aluminium Hydride;(3) to being equipped with in the reactor of Lithium Aluminium Hydride, add oxolane liquid, stirring and dissolving obtains the tetrahydrofuran solution of Lithium Aluminium Hydride, and the concentration that makes Lithium Aluminium Hydride in solution is 2.5wt%～15wt%;(4) take hydrophilic nano CaCO 3and glucose, be added in 100mL deionized water, ultrasonic vibration mix 30 minutes, make glucose dissolve and with nanometer CaCO 3be uniformly dispersed, heating evaporates the water, and then at 160 DEG C, solidifies 6 hours, obtains cured product; Again cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours, obtains carbonized product and is cooled to 20 DEG C; Carbonized product is washed with hydrochloric acid and the deionized water of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains macropore material with carbon element at 120 DEG C;Wherein, hydrophilic nano CaCO 3with the mass ratio of water soluble starch be 1: 1, and hydrophilic nano CaCO 3addition be that the addition of 10g and glucose is 10g;(5) get the tetrahydrofuran solution that the macropore material with carbon element making in step (4) adds the Lithium Aluminium Hydride obtaining in step (3), after ultrasonic mixing 30min, evaporate oxolane, obtain the carbon-supported Lithium Aluminium Hydride composite material of macropore;(6) carbon-supported the macropore making in step (5) Lithium Aluminium Hydride composite material is placed in to reactor, at 400 DEG C, vacuumize after 4 hours, obtain the carbon-supported aluminium lithium composite of macropore material, and carbon-supported macropore aluminium lithium composite material is cooled to 20 DEG C;(7) get perfluorinated sulfonic resin 10g and be placed in the 100mL LiOH aqueous solution, at 80 DEG C, stir after 2 hours, filter and obtain product; Take out product and with after washed with de-ionized water, carry out vacuumize, obtain Li +type perfluorinated sulfonic resin;Get again the Li that 10g makes +type perfluorinated sulfonic resin is dissolved in 200mL 1-METHYLPYRROLIDONE (NMP), obtains Li +type perfluor sulfoacid resin solution;(8), in the glove box of argon gas atmosphere, get the Li making in step (7) +type perfluor sulfoacid resin solution is added in the carbon-supported aluminium lithium composite of the macropore material making in step (6), after stirring at 150 DEG C evaporate to dryness, obtain the carbon-supported Li of macropore +type perfluorinated sulfonic resin is coated Al-Li Alloy Matrix Composites;Wherein, Li +the addition of type perfluor sulfoacid resin solution is 50～200mL, and the addition of the carbon-supported aluminium lithium composite of macropore material is 1g.
- 2. the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material according to claim 1, is characterized in that, in the glove box of described argon gas atmosphere, water content and oxygen content are all less than 1ppm.
- 3. the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material according to claim 1, is characterized in that, the perfluorinated sulfonic resin in described step (7) adopts film or pulverous perfluorinated sulfonic resin.
- 4. the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material according to claim 1, is characterized in that, the LiOH aqueous solution in described step (7) is that mass concentration is the LiOH aqueous solution of 10wt%.
- 5. the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material according to claim 1, is characterized in that, described hydrophilic nano CaCO 3particle diameter be 15～40nm.
- 6. the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material according to claim 1, it is characterized in that, hydrogenation plant in described step (1), comprises pressure-reducing valve, high-purity High Pressure Hydrogen bottle, hydrogen storehouse, Pressure gauge, unidirectional stop valve, vacuum pump, pipeline docking adapter, vacuum meter;High-purity High Pressure Hydrogen bottle (1-1), pressure-reducing valve (1-6), hydrogen storehouse (1-3), unidirectional stop valve (1-10) connect successively, are connected with Pressure gauge (1-11) on hydrogen storehouse (1-3); Between hydrogen storehouse (1-3) and unidirectional stop valve (1-10), be connected with unidirectional stop valve (1-9), unidirectional stop valve (1-9) is connected with vacuum pump (1-4), between unidirectional stop valve (1-9) and vacuum pump (1-4), is also connected with vacuum meter (1-12); Hydrogen storehouse (1-3) is also connected with unidirectional stop valve (1-8), and unidirectional stop valve (1-8) is connected with pipeline docking adapter (1-5);Reactor is connected with unidirectional stop valve (1-7), and is connected with the pipeline docking adapter (1-5) in hydrogenation plant by unidirectional stop valve (1-7).
- 7. the preparation method of Li ion type perfluoro sulfonate resin metallized aluminum Zinc-lithium alloy material according to claim 1, is characterized in that, the intensification of described reactor is heated by reactor is arranged in electric furnace, utilizes the heating of electric furnace to realize.
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| CN104592541A (en) * | 2015-01-20 | 2015-05-06 | 浙江大学 | Microporous polybenzimidazole membrane and lithium-sulfur battery with modified polybenzimidazole as membrane |
| CN105514374A (en) * | 2015-12-11 | 2016-04-20 | 武汉理工大学 | Graphitized carbon coated manganese-fluorine oxide material and preparation method thereof |
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| CN1442916A (en) * | 2003-03-28 | 2003-09-17 | 中国科学院上海微***与信息技术研究所 | Silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its preparation method |
| CN101759858A (en) * | 2008-11-14 | 2010-06-30 | 杨玉生 | Preparation method of high-boiling point salt type perfluor sulfoacid resin solution |
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| CN105514374A (en) * | 2015-12-11 | 2016-04-20 | 武汉理工大学 | Graphitized carbon coated manganese-fluorine oxide material and preparation method thereof |
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