CN102903540A - Electrochemical capacitor - Google Patents
Electrochemical capacitor Download PDFInfo
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- CN102903540A CN102903540A CN2012103963384A CN201210396338A CN102903540A CN 102903540 A CN102903540 A CN 102903540A CN 2012103963384 A CN2012103963384 A CN 2012103963384A CN 201210396338 A CN201210396338 A CN 201210396338A CN 102903540 A CN102903540 A CN 102903540A
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Abstract
The invention provides an electrochemical capacitor, which comprises an anode, a cathode, an electrolyte and a diaphragm, wherein the electrolyte is mixed electrolyte consisting of sodium salt and lithium salt; and the cathode is optionally made of sodium titanate nanotubes or sodium titanate nanotubes/ carbon composite materials. The sodium salt and the lithium salt are mixed to form the electrolyte, and the cathode is made of the sodium titanate nanotubes or sodium titanate nanotubes/carbon composite materials, so that the cost of the capacitor is reduced, diffusion of ions is facilitated, the ions can be quickly embedded in the capacitor or separated from the capacitor conveniently, and the electrochemical capacitor has high energy density and power density. An electrochemical experiment proves that after the capacitor with the cathode made of the sodium titanate nanotubes or the sodium titanate nanotubes/the carbon composite materials is recycled for 100 times under the work voltage of 0-3.5V, the specific capacity of the capacitor is about 95%.
Description
Technical field
The present invention relates to the capacitor technology field, relate in particular to a kind of electrochemical capacitor.
Background technology
Electrochemical capacitor claims again ultracapacitor, is comprised of positive pole, negative pole, electrolyte and the barrier film between positive pole and negative pole.Electrochemical capacitor is a kind of novel electrochemical energy storage and conversion equipment, have that power density is high, the time that discharges and recharges is short, good cycle, long service life and be convenient to the advantages such as maintenance, be widely used in fields such as national defence, space flight and aviation, auto industry, consumer electronics, telecom communication, electric power and railways, can be used as accessory power supply, stand-by power supply, main power source and replacement power supply such as it, it can form with battery " the dense form ultra high power pulse power " in the military affairs, and the especially big operate power of MW level is provided for microwave weapon and laser weapon.Along with the continuous expansion of range of application, electrochemical capacitor is regarded as one of most promising new green power in this century.
Although electrochemical capacitor has higher power density, its energy density is lower, has limited it and has further developed.In order to improve the energy density of electrochemical capacitor, the researcher is studied its electrode material, and discovery can be mated the electrode material of two kinds of different electrochemical mechanisms, forms asymmetric capacitor, greatly improves its energy density.Prior art discloses uses carbon nano-tube as the technology of negative material, and this technology has improved charge/discharge capacity and the cyclical stability of battery, but the first charge-discharge efficiency of carbon nano-tube is lower, can not well improve the energy density of capacitor.
Research is found, carbon nano-tube is mixed the formation composite carbon negative polar material with graphite, can overcome carbon nano-tube separately as the shortcoming of negative material, wherein less carbon nanomaterial is filled larger graphite granule hole, can form good conductive network, but the surface activity of carbon nano-tube is higher, is difficult for Uniform Dispersion during with the standby combination electrode material of graphite-made, has affected the further application of material.Also have the researcher with the lithium composite material as negative material, the introducing of lithium composite material so that the energy density of this class asymmetric capacitor greatly improve.Yet lithium is as a kind of rare metal of occurring in nature, and its content is limited, so the cost of this class capacitor is very high.The researcher has also announced and has adopted sodium titanate as the technology of negative material, this technology adopts neutral sodium-salt organic solution as electrolyte, because the sodium ion size is larger, so its embedding and to deviate from process slower, the further raising of capacitor energy density affected.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of electrochemical capacitor, has higher power density and energy density and cycle life preferably.
The invention provides a kind of electrochemical capacitor, comprise: positive pole, negative pole, electrolyte and barrier film, described electrolyte is the mixed electrolytic solution of sodium salt and lithium salts, and described negative material is selected from any one in sodium titanate nanotubes or the sodium titanate nanotubes/carbon composite.
Preferably, described sodium titanate nanotubes/carbon composite prepares in accordance with the following methods: in sodium hydroxide solution after the hybrid reaction, roasting obtains sodium titanate nanotubes/carbon composite with sodium titanate nanotubes and carbon-source cpd.
Preferably, the mass ratio of described sodium titanate nanotubes and carbon-source cpd is 1:0.5 ~ 2.
Preferably, described carbon-source cpd is selected from any one or a few in glucose, sucrose, citric acid or the vitamin C.
Preferably, the temperature of described roasting is 400 ℃ ~ 900 ℃, and the time of roasting is 4h ~ 5h.
Preferably, in the described mixed electrolytic solution, the total concentration of sodium ion and lithium ion is 0.5mol/L ~ 1.5mol/L.
Preferably, in the described mixed electrolytic solution, the mol ratio of sodium ion and lithium ion is (8 ~ 1): (1 ~ 8).
Preferably, described sodium salt is selected from any one or a few in sodium tetrafluoroborate, sodium hexafluoro phosphate and the sodium perchlorate.
Preferably, described lithium salts is selected from any one or a few in LiBF4, lithium hexafluoro phosphate and the lithium perchlorate.
Preferably, the solvent of described electrolyte is selected from one or more in propene carbonate, ethylene carbonate, diethyl carbonate and the dimethyl carbonate.
Electrochemical capacitor provided by the invention, its electrolyte is the mixed electrolytic solution of sodium salt and lithium salts, negative material adopts sodium titanate nanotubes or sodium titanate nanotubes/carbon composite, wherein, lithium salts and sodium salt mix as electrolyte, simultaneously with sodium titanate nanotubes or sodium titanate nanotubes/carbon composite as negative material, not only reduced the cost of capacitor, and be conducive to the diffusion of ion, be convenient to ion and embed fast and deviate from, thereby make electrochemical capacitor have higher energy density and power density.Simultaneously, the embedding of ion only occurs and deviates from electrochemical capacitor provided by the invention in charge and discharge process, other chemical reaction does not occur, and electrode structure does not change, and therefore has preferably cycle life.
Experiment shows, electrochemical capacitor provided by the invention, under the operating voltage of 0V ~ 4V, first discharge specific capacity is 60mAh/g ~ 100mAh/g, the capacitor of preparation take sodium titanate nanotubes as negative material, under the operating voltage of 0V ~ 3V, circulate after 1000 times, its specific capacity is about 85%, the capacitor of preparation take sodium titanate nanotubes/carbon composite as negative material, under the operating voltage of 0V ~ 3.5V, circulate after 100 times, its specific capacity is about 95%.
Description of drawings
Fig. 1 is the sodium titanate nanotubes of embodiment of the invention preparation and the X-ray diffractogram of sodium titanate nanotubes/carbon composite;
Fig. 2 is the transmission electron microscope picture of the sodium titanate nanotubes of the embodiment of the invention 8 preparations;
Fig. 3 is the transmission electron microscope picture of the sodium titanate nanotubes/carbon composite of the embodiment of the invention 9 preparations;
Fig. 4 is the specific capacitance of single electrode curve chart of battery under the operating voltage of 0V ~ 4V of the embodiment of the invention 10 ~ 16 preparations;
Fig. 5 be the battery of the embodiment of the invention 10 ~ 16 preparation in the operating voltage of 0V ~ 4V, corresponding energy density curve when discharging and recharging under the current density of 0.083A/g;
Fig. 6 be the battery of the embodiment of the invention 10 ~ 16 preparation in the operating voltage of 0V ~ 4V, corresponding power density curve when discharging and recharging under the current density of 0.083A/g;
Fig. 7 is the specific capacitance of single electrode curve chart of battery under the operating voltage of 0V ~ 3V of the embodiment of the invention 17 ~ 23 preparations;
Fig. 8 is the cyclic curve figure of battery under the operating voltage of 0V ~ 3V of the embodiment of the invention 17 ~ 23 preparations;
Fig. 9 be the battery of the embodiment of the invention 17 ~ 23 preparation in the operating voltage of 0V ~ 3V, corresponding energy density curve when discharging and recharging under the current density of 0.167A/g;
Figure 10 be the battery of the embodiment of the invention 17 ~ 23 preparation in the operating voltage of 0V ~ 3V, corresponding power density curve when discharging and recharging under the current density of 0.167A/g;
Figure 11 be the battery of the embodiment of the invention and comparative example preparation under the operating voltage of 0V ~ 3.5V, the cyclic curve figure under the current density of 0.083A/g.
Embodiment
The invention provides a kind of electrochemical capacitor, comprise: positive pole, negative pole, electrolyte and barrier film, wherein said electrolyte is the mixed electrolytic solution of sodium salt and lithium salts, and described negative material is selected from any one in sodium titanate nanotubes or the sodium titanate nanotubes/carbon composite.
Electrochemical capacitor provided by the invention, its electrolyte is the mixed electrolytic solution of sodium salt and lithium salts, negative material adopts sodium titanate nanotubes or sodium titanate nanotubes/carbon composite, wherein, lithium salts and sodium salt mix as electrolyte, simultaneously with sodium titanate nanotubes or sodium titanate nanotubes/carbon composite as negative material, not only reduced the cost of capacitor, and more be conducive to the diffusion of ion, be convenient to ion and embed fast and deviate from, thereby make electrochemical capacitor have higher energy density and power density.
Capacitor provided by the invention, comprise: positive pole, negative pole, electrolyte and barrier film, the present invention does not have specific (special) requirements to the structure of the capacitor that provides, can be structure well known to those skilled in the art, comprise positive pole, negative pole and the barrier film between both positive and negative polarity, barrier film and positive and negative electrode all are dipped in the described mixed electrolytic solution.
The present invention does not have specific (special) requirements to the positive electrode of described electrochemical capacitor, can be positive electrode well known to those skilled in the art, is preferably graphite or active carbon.
The present invention there is no specific (special) requirements to the diaphragm material between the described electrochemical capacitor both positive and negative polarity, can for diaphragm material well known to those skilled in the art, be preferably glass fibre.
Electrochemical capacitor provided by the invention, its electrolyte are the mixed electrolytic solution of sodium salt and lithium salts.
Described sodium salt is preferably neutral sodium-salt, more preferably any one or a few in sodium tetrafluoroborate, sodium hexafluoro phosphate and the sodium perchlorate.Described lithium salts is preferably neutral lithium salts, more preferably any one or a few in LiBF4, lithium hexafluoro phosphate and the lithium perchlorate.Above-mentioned lithium salts and sodium salt all have larger solubility in organic solution, and more stable, so that electrolyte intermediate ion concentration is larger, thereby can provide more free ion for electrolyte, finally are conducive to improve the performance of electrochemical capacitor.
In the mixed electrolytic solution of sodium salt of the present invention and lithium salts, the total ion concentration of sodium ion and lithium ion is preferably 0.5mol/L ~ 1.5mol/L, more preferably 0.5mol/L ~ 1.2mol/L.The concentration of described sodium salt and lithium salts can not be too high, and too high concentration can cause the viscosity of electrolyte to increase, and is unfavorable for that reaction occurs to embed and deviate from ion fast transferring to electrode surface.
Among the present invention, in the mixed electrolytic solution of described sodium salt and lithium salts, the mol ratio of sodium ion and lithium ion is preferably (8 ~ 1): (1 ~ 8), more preferably (4 ~ 1): (1 ~ 4).
Among the present invention, the solvent of described electrolyte is preferably one or more in propene carbonate, ethylene carbonate, diethyl carbonate and the dimethyl carbonate.Above-mentioned solvent has lower viscosity, so that the ion in the electrolyte has faster migration velocity, and described solvent has moderate conductance and wider electrochemical window, thereby is conducive to improve energy density and the power density of electrochemical capacitor.
The present invention is take sodium salt and lithium salts as mixed electrolytic solution, and wherein, sodium ion and lithium ion cooperatively interact, more be conducive to the diffusion of ion, be convenient to ion and embed fast and deviate from, thereby make electrochemical capacitor have higher energy density and power density, also saved cost simultaneously.
Electrochemical capacitor provided by the invention, its negative material is preferably any one in sodium titanate nanotubes or the sodium titanate nanotubes/carbon composite, more preferably sodium titanate nanotubes/carbon composite.
The present invention does not have particular restriction to the source of described sodium titanate nanotubes, can make by oneself for generally commercially available, preferably in accordance with the following methods preparation yet:
Obtain solid particle after titanium dioxide mixed, reacts with sodium hydroxide solution;
Obtain sodium titanate nanotubes after described solid particle calcined.
Among the present invention, there is no specific (special) requirements for the source of titanium dioxide, can be for generally commercially available.Described sodium hydroxide solution is preferably sodium hydrate aqueous solution, and its concentration is preferably 5mol/L ~ 15mol/L, more preferably 7mol/L ~ 12mol/L.
At first titanium dioxide is mixed, reacts with sodium hydroxide solution, described reaction condition is preferably stirring at room, and described mixing time is preferably 0.5h ~ 3h.After the stirring at room, again product is carried out hydro-thermal reaction, the temperature of described hydro-thermal reaction is preferably 100 ℃ ~ 300 ℃, more preferably 130 ℃ ~ 200 ℃; The time of described hydro-thermal reaction is preferably 24h ~ 90h, more preferably 30h ~ 60h.
After carrying out hydro-thermal reaction, reaction system is cooled to room temperature, obtains suspension-turbid liquid, with described suspension-turbid liquid with intermediate water wash to the pH value be 5 ~ 9, then carry out centrifugation, and dry, obtain solid particle.The present invention all without specific (special) requirements, can be the method and apparatus of centrifugation well known to those skilled in the art to the method and apparatus of described centrifugation.The present invention there is no specific (special) requirements to the method and apparatus of described drying, can be the method and apparatus of drying well known to those skilled in the art, the present invention preferably adopts drying box to carry out drying, and the temperature of described drying is preferably 60 ℃ ~ 100 ℃, and the time of described drying is preferably 24h ~ 48h.
After obtaining solid particle, described solid particle is calcined, obtained sodium titanate nanotubes, the temperature of described calcining is preferably 200 ℃ ~ 1200 ℃, and more preferably 400 ℃ ~ 900 ℃, the time of described calcining is preferably 2h ~ 8h, more preferably 4h ~ 5h.
The sodium titanate of the nano tubular structure that the present invention adopts, has the channel design of larger specific area, opening and shorter diffusion length, can reduce the distance that the electrolyte intermediate ion diffuses to electrode surface, thereby more be conducive to the diffusion of ion, and be convenient to ion and embed fast and deviate from, thereby make electrochemical capacitor have higher energy density and power density.
In the present invention, described sodium titanate nanotubes/carbon composite is in accordance with the following methods preparation preferably: in sodium hydroxide solution after the hybrid reaction, roasting obtains sodium titanate nanotubes/carbon composite with sodium titanate nanotubes and carbon-source cpd.
At first the hybrid reaction in sodium hydroxide solution with sodium titanate nanotubes and carbon-source cpd obtains solid product.The present invention there is no specific (special) requirements to the source of described sodium titanate nanotubes, can for generally commercially available, also can make by oneself according to the preparation method of above-mentioned sodium titanate nanotubes.Among the present invention, described carbon-source cpd is preferably any one or a few in glucose, sucrose, citric acid or the vitamin C, more preferably glucose.The present invention there is no specific (special) requirements to the source of described carbon-source cpd, can be for generally commercially available.Described sodium hydroxide solution is preferably the aqueous solution of NaOH, and its concentration is preferably 0.05mol/L ~ 1mol/L, more preferably 0.1mol/L ~ 0.5mol/L.The mass ratio of described sodium titanate nanotubes and carbon-source cpd is preferably 1:0.5 ~ 2, more preferably 1:0.7 ~ 1.2.The temperature of described reaction is preferably 100 ℃ ~ 200 ℃, more preferably 140 ℃ ~ 180 ℃.
After obtaining solid product, described solid product is washed, after dry, the roasting, obtains sodium titanate nanotubes/carbon composite.Wherein, the present invention there is no specific (special) requirements to described washing, dry method and apparatus, can be the method and apparatus of washing well known to those skilled in the art, drying.The temperature of described roasting is preferably 200 ℃ ~ 1000 ℃, and more preferably 400 ℃ ~ 900 ℃, the time of roasting is preferably 2h ~ 7h, more preferably 4h ~ 5h.Described roasting is preferably under argon shield to be carried out.Adopt sodium titanate nanotubes/carbon composite as negative material, its preparation method is simple, and low price is conducive to reduce the cost of electrochemical capacitor.Simultaneously the ion that is conducive in the electrolyte of nano tubular structure spreads, and it is embedded fast and deviates from, thereby be conducive to improve energy density and the power density of electrochemical capacitor.
Electrochemical capacitor provided by the invention is carried out electrochemical property test, the result shows, electrochemical capacitor provided by the invention, under the operating voltage of 0V ~ 4V, first discharge specific capacity is 60mAh/g ~ 100mAh/g, the capacitor of preparation take sodium titanate nanotubes as negative material, under the operating voltage of 0V ~ 3V, circulate after 1000 times, its specific capacity is about 85%, and the capacitor of preparation take sodium titanate nanotubes/carbon composite as negative material is under the operating voltage of 0V ~ 3.5V, circulate after 100 times, its specific capacity is about 95%.
Electrochemical capacitor provided by the invention, its electrolyte is the mixed electrolytic solution of sodium salt and lithium salts, negative material adopts sodium titanate nanotubes or sodium titanate nanotubes/carbon composite, wherein, lithium salts and sodium salt mix as electrolyte, simultaneously with sodium titanate nanotubes or sodium titanate nanotubes/carbon composite as negative material, not only reduced the cost of capacitor, and more be conducive to the diffusion of ion, be convenient to ion and embed fast and deviate from, thereby make electrochemical capacitor have higher energy density and power density.Simultaneously, the embedding of ion only occurs and deviates from electrochemical capacitor provided by the invention in charge and discharge process, other chemical reaction does not occur, and electrode structure does not change, and therefore has preferably cycle life.
In order to further specify the present invention, below in conjunction with embodiment electrochemical capacitor provided by the invention is described in detail.
Be the NaPF of 1mol/L with concentration
6Carbonic allyl ester solution and concentration are the LiPF of 1mol/L
6Carbonic allyl ester solution is 4:1 respectively by volume, 3:1, and 2:1,1:1,1:2, the ratio of 1:3 and 1:4 mixes, and obtains respectively mixed electrolytic solution.The results are shown in Table 1, table 1 is that the mol ratio of sodium ion, lithium ion gathers in the mixed electrolytic solution of embodiment 1 ~ 7 preparation.
In the mixed electrolytic solution of table 1 embodiment 1 ~ 7 preparation, the mol ratio of sodium ion, lithium ion gathers
| |
1 | 2 | 3 | 4 | 5 | 6 | 7 |
| n(Na):n(Li) | 4：1 | 3：1 | 2：1 | 1：1 | 1：2 | 1：3 | 1：4 |
Embodiment 8
NaOH aqueous solution with 1g titanium dioxide and 80mL 10mol/L, stir the reactor that changes 100mL after 1 hour under the room temperature, be heated to 150 ℃ and carried out hydro-thermal reaction 48 hours, then product is cooled to room temperature, and with intermediate water wash to the pH value be 8, product after the washing is carried out centrifugation obtain solid particle, the solid particle dry 40h in 80 ℃ drying box that obtains is obtained dry solid particle, then the solid particle of drying is calcined 5h in 600 ℃ air atmosphere, obtain sodium titanate nanotubes, be designated as NTO.
Sodium titanate nanotubes to embodiment 8 preparations carries out X-ray diffraction analysis, adopt Rigaku D/max-IIB type diffractometer, Cu target K alpha ray is made X-ray source, sweep limits is 5 ° ~ 80 °, sweep speed is 1 °/min, contrast PDF data card, obtain the X-ray diffractogram of sodium titanate nanotubes, the results are shown in Figure 1, Fig. 1 is the sodium titanate nanotubes of embodiment of the invention preparation and the X-ray diffractogram of sodium titanate nanotubes/carbon composite, wherein, curve a is the X-ray diffractogram of the sodium titanate nanotubes of the embodiment of the invention 8 preparations, and characteristic peak marks in the drawings.As shown in Figure 1, NTO is typical layered titanate structure, proves that method provided by the invention can successfully prepare sodium titanate nanotubes.
Sodium titanate nanotubes to embodiment 8 preparations carries out the detection of pattern and composition, the XL-30ESEM type scanning electron microscopy of employing PHILIPS Co. characterizes pattern and the composition of sodium titanate nanotubes, accelerating voltage is 15kV, experimental result is seen Fig. 2, Fig. 2 is the transmission electron microscope picture of the sodium titanate nanotubes of the embodiment of the invention 8 preparations, the sodium titanate provided by the invention hollow sodium mitron that is length between hundreds of nanometers to a micron as shown in Figure 2, caliber is approximately between 6 ~ 10 nanometers.
Embodiment 9
NTO and the 0.5g glucose of 0.5g embodiment 8 preparations are mixed also ultrasonic dispersion in the sodium hydrate aqueous solution of 40mL 0.1mol/L; then being heated to 160 ℃ reacts; obtain solid product; with solid product wash, after the drying; under argon shield, be heated to 600 ℃ and carry out roasting 5h; prepare sodium titanate nanotubes/carbon composite, be designated as NTO-C.
Sodium titanate nanotubes/carbon composite to embodiment 9 preparations carries out X-ray diffraction analysis, adopt Rigaku D/max-IIB type diffractometer, Cu target K alpha ray is made X-ray source, sweep limits is 5 ° ~ 80 °, sweep speed is 1 °/min, contrast PDF data card, obtain the X-ray diffractogram of sodium titanate nanotubes/carbon composite, the results are shown in Figure 1, Fig. 1 is the sodium titanate nanotubes of embodiment of the invention preparation and the X-ray diffractogram of sodium titanate nanotubes/carbon composite, wherein, curve b is the X-ray diffractogram of the sodium titanate nanotubes/carbon composite of the embodiment of the invention 9 preparations, and characteristic peak marks in the drawings.As shown in Figure 1, NTO-C is typical layered titanate structure, and method provided by the invention can successfully prepare sodium titanate nanotubes/carbon composite.
Sodium titanate nanotubes/carbon composite to embodiment 9 preparations carries out the detection of pattern and composition, the XL-30ESEM type scanning electron microscopy of employing PHILIPS Co. is used for characterizing pattern and the composition of sodium titanate nanotubes, accelerating voltage is 15kV, experimental result is seen Fig. 3, Fig. 3 is the transmission electron microscope picture of the sodium titanate nanotubes/carbon composite of the embodiment of the invention 9 preparations, sodium titanate nanotubes/carbon composite is nano tubular structure as shown in Figure 3, and the surface has coated one deck carbon film.
Stainless steel battery current collecting compressing tablet film forming also on the net will be coated in behind the sodium titanate nanotubes of 6mg embodiment 8 preparation and the 3mg electroconductive binder mixing, then being heated to 180 ℃ of vacuumizes changes over to after 3 hours in the saturated glove box of anhydrous and oxygen-free argon gas as negative pole, adopt same procedure, anodal as raw material prepares take 6mg graphite and 3mg electroconductive binder, respectively with the mixed electrolytic solution of embodiment 1 ~ 7 preparation as electrolyte, take two glass fibres as barrier film, be assembled into button cell.
Battery to embodiment 10 ~ 16 preparations carries out electrochemical property test, and test result is seen Fig. 4, Fig. 5 and Fig. 6.Fig. 4 is the specific capacitance of single electrode curve chart of battery under the operating voltage of 0V ~ 4V of the embodiment of the invention 10 ~ 16 preparations, wherein a curve is embodiment 10 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 4:1, a ' curve is its single electrode specific discharge capacity curve; The b curve is embodiment 11 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 3:1, b ' curve is its single electrode specific discharge capacity curve; The c curve is embodiment 12 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 2:1, c ' curve is its single electrode specific discharge capacity curve; The d curve is embodiment 13 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:1, d ' curve is its single electrode specific discharge capacity curve; The e curve is embodiment 14 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:2, e ' curve is its single electrode specific discharge capacity curve; The f curve is embodiment 15 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:3, f ' curve is its single electrode specific discharge capacity curve; The g curve is embodiment 16 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:4, g ' curve is its single electrode specific discharge capacity curve.Fig. 5 be the battery of the embodiment of the invention 10 ~ 16 preparation in the operating voltage of 0V ~ 4V, corresponding energy density curve when discharging and recharging under the current density of 0.083A/g.Fig. 6 be the battery of the embodiment of the invention 10 ~ 16 preparation in the operating voltage of 0V ~ 4V, corresponding power density curve when discharging and recharging under the current density of 0.083A/g.By Fig. 4, Fig. 5 and Fig. 6 as can be known, mixed electrolytic solution battery provided by the invention has higher capacitance in charge and discharge process.
Embodiment 17 ~ 23
Stainless steel battery current collecting compressing tablet film forming also on the net will be coated in behind the sodium titanate nanotubes of 6mg embodiment 8 preparation and the 3mg electroconductive binder mixing, then being heated to 180 ℃ of vacuumizes changes over to after 3 hours in the saturated glove box of anhydrous and oxygen-free argon gas as negative pole, adopt same procedure, anodal as raw material prepares take 6mg active carbon and 3mg electroconductive binder, respectively with the mixed electrolytic solution of embodiment 1 ~ 7 preparation as electrolyte, take two glass fibres as barrier film, be assembled into button cell.
Battery to embodiment 17 ~ 23 preparations carries out electrochemical property test, and test result is seen Fig. 7, Fig. 8, Fig. 9 and Figure 10.Fig. 7 is the specific capacitance of single electrode curve chart of battery under the operating voltage of 0V ~ 3V of the embodiment of the invention 17 ~ 23 preparations, wherein a curve is embodiment 17 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 4:1, a ' curve is its single electrode specific discharge capacity curve; The b curve is embodiment 18 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 3:1, b ' curve is its single electrode specific discharge capacity curve; The c curve is embodiment 19 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 2:1, c ' curve is its single electrode specific discharge capacity curve; The d curve is embodiment 20 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of 1: 1 battery, d ' curve is its single electrode specific discharge capacity curve; The e curve is embodiment 21 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:2, e ' curve is its single electrode specific discharge capacity curve; The f curve is embodiment 22 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:3, f ' curve is its single electrode specific discharge capacity curve; The g curve is embodiment 23 preparations, n(Na in the mixed electrolytic solution): n(Li) be the single electrode charge ratio capacity curve of the battery of 1:4, g ' curve is its single electrode specific discharge capacity curve.Fig. 8 is the cyclic curve figure of battery under the operating voltage of 0V ~ 3V of the embodiment of the invention 17 ~ 23 preparations, wherein, the a curve is the cyclic curve figure of the battery of embodiment 17 preparations, the b curve is the cyclic curve figure of the battery of embodiment 18 preparations, the c curve is the cyclic curve figure of the battery of embodiment 19 preparations, the d curve is the cyclic curve figure of the battery of embodiment 20 preparations, the e curve is the cyclic curve figure of the battery of embodiment 21 preparations, the f curve is the cyclic curve figure of the battery of embodiment 22 preparations, and the g curve is the cyclic curve figure of the battery of embodiment 23 preparations.Fig. 9 be the battery of the embodiment of the invention 17 ~ 23 preparation in the operating voltage of 0V ~ 3V, corresponding energy density curve when discharging and recharging under the current density of 0.167A/g.Figure 10 be the battery of the embodiment of the invention 17 ~ 23 preparation in the operating voltage of 0V ~ 3V, corresponding power density curve when discharging and recharging under the current density of 0.167A/g.By Fig. 7, Fig. 8, Fig. 9 and Figure 10 as can be known, mixed electrolytic solution battery provided by the invention has higher capacitance and cycle performance preferably in charge and discharge process.
Embodiment 24
Stainless steel battery current collecting compressing tablet film forming also on the net will be coated in behind the sodium titanate nanotubes/carbon composite of 6mg embodiment 9 preparation and the 3mg electroconductive binder mixing, then being heated to 180 ℃ of vacuumizes changes over to after 3 hours in the saturated glove box of anhydrous and oxygen-free argon gas as negative pole, adopt same procedure, anodal as raw material prepares take 6mg graphite and 3mg electroconductive binder, with among the embodiment 4 preparation mixed electrolytic solution as electrolyte, take two glass fibres as barrier film, be assembled into button cell.
Battery to embodiment 24 preparations carries out electro-chemical test, the results are shown in Figure 11, Figure 11 is that the battery of the embodiment of the invention and comparative example preparation is under the operating voltage of 0V ~ 3.5V, 0.083A/g current density under cyclic curve figure, wherein, curve c is the cyclic curve figure of the battery of the embodiment of the invention 24 preparations.
Comparative example 1 ~ 2
Stainless steel battery current collecting compressing tablet film forming also on the net will be coated in behind the sodium titanate nanotubes/carbon composite of 6mg embodiment 9 preparation and the 3mg electroconductive binder mixing, then being heated to 180 ℃ of vacuumizes changes over to after 3 hours in the saturated glove box of anhydrous and oxygen-free argon gas as negative pole, adopt same procedure, preparation is anodal take 6mg graphite and 3mg electroconductive binder as raw material, respectively the LiPF take concentration as 1mol/L
6Carbonic allyl ester solution and concentration are the NaPF of 1mol/L
6Carbonic allyl ester solution take two glass fibres as barrier film, is assembled into button cell as electrolyte.
Battery to comparative example 1 ~ 2 preparation carries out electro-chemical test, the results are shown in Figure 11, Figure 11 is that the battery of the embodiment of the invention and comparative example preparation is under the operating voltage of 0V ~ 3.5V, 0.083A/g current density under cyclic curve figure, wherein, curve a is the cyclic curve figure of the battery of comparative example 1 preparation of the present invention, and curve b is the cyclic curve figure of the battery of comparative example 2 preparations of the present invention.
As shown in Figure 11, the mixed electrolytic solution electrochemical capacitor is than using separately neutral lithium salts or neutral sodium-salt to have higher capacitance as the electrochemical capacitor of electrolyte, namely have higher energy density, and lower than using separately the electrochemical capacitor cost of neutral lithium salts.
By above-described embodiment and comparative example as can be known, electrochemical capacitor provided by the invention, take the mixed electrolytic solution of sodium salt and lithium salts as electrolyte, adopting sodium titanate nanotubes or sodium titanate nanotubes/carbon composite is negative material, has higher power density and energy density and cycle life preferably.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. electrochemical capacitor, comprise: positive pole, negative pole, electrolyte and barrier film, it is characterized in that, described electrolyte is the mixed electrolytic solution of sodium salt and lithium salts, and described negative material is selected from any one in sodium titanate nanotubes or the sodium titanate nanotubes/carbon composite.
2. electrochemical capacitor according to claim 1, it is characterized in that, described sodium titanate nanotubes/carbon composite prepares in accordance with the following methods: in sodium hydroxide solution after the hybrid reaction, roasting obtains sodium titanate nanotubes/carbon composite with sodium titanate nanotubes and carbon-source cpd.
3. electrochemical capacitor according to claim 2 is characterized in that, the mass ratio of described sodium titanate nanotubes and carbon-source cpd is 1:0.5 ~ 2.
4. electrochemical capacitor according to claim 2 is characterized in that, described carbon-source cpd is selected from any one or a few in glucose, sucrose, citric acid or the vitamin C.
5. electrochemical capacitor according to claim 2 is characterized in that, the temperature of described roasting is 400 ℃ ~ 900 ℃, and the time of roasting is 4h ~ 5h.
6. electrochemical capacitor according to claim 1 is characterized in that, in the described mixed electrolytic solution, the total concentration of sodium ion and lithium ion is 0.5mol/L ~ 1.5mol/L.
7. electrochemical capacitor according to claim 1 is characterized in that, in the described mixed electrolytic solution, the mol ratio of sodium ion and lithium ion is (8 ~ 1): (1 ~ 8).
8. electrochemical capacitor according to claim 1 is characterized in that, described sodium salt is selected from any one or a few in sodium tetrafluoroborate, sodium hexafluoro phosphate and the sodium perchlorate.
9. electrochemical capacitor according to claim 1 is characterized in that, described lithium salts is selected from any one or a few in LiBF4, lithium hexafluoro phosphate and the lithium perchlorate.
10. method according to claim 1 is characterized in that, the solvent of described electrolyte is selected from one or more in propene carbonate, ethylene carbonate, diethyl carbonate and the dimethyl carbonate.
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| CN104616901A (en) * | 2015-01-27 | 2015-05-13 | 上海奥威科技开发有限公司 | Sodium ion super capacitor and preparation method thereof |
| CN108630441A (en) * | 2018-04-28 | 2018-10-09 | 南京林业大学 | A kind of biomass graded porous carbon supporting nanostructures sodium titanate and preparation method thereof |
| CN109637817A (en) * | 2018-12-20 | 2019-04-16 | 电子科技大学 | A kind of mixed ionistor and preparation method thereof |
| CN110164712A (en) * | 2019-06-20 | 2019-08-23 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of lithium-ion capacitor electrode material and preparation method thereof |
| CN113692668A (en) * | 2018-12-17 | 2021-11-23 | 株式会社Lg新能源 | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same |
| CN114751391A (en) * | 2022-04-11 | 2022-07-15 | 长沙理工大学 | High-density phosphorylated sodium titanate material, preparation method and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104616901A (en) * | 2015-01-27 | 2015-05-13 | 上海奥威科技开发有限公司 | Sodium ion super capacitor and preparation method thereof |
| CN108630441A (en) * | 2018-04-28 | 2018-10-09 | 南京林业大学 | A kind of biomass graded porous carbon supporting nanostructures sodium titanate and preparation method thereof |
| CN113692668A (en) * | 2018-12-17 | 2021-11-23 | 株式会社Lg新能源 | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same |
| CN109637817A (en) * | 2018-12-20 | 2019-04-16 | 电子科技大学 | A kind of mixed ionistor and preparation method thereof |
| CN110164712A (en) * | 2019-06-20 | 2019-08-23 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of lithium-ion capacitor electrode material and preparation method thereof |
| CN110164712B (en) * | 2019-06-20 | 2021-06-01 | 上海大学(浙江·嘉兴)新兴产业研究院 | Lithium ion capacitor electrode material and preparation method thereof |
| CN114751391A (en) * | 2022-04-11 | 2022-07-15 | 长沙理工大学 | High-density phosphorylated sodium titanate material, preparation method and application |
| CN114751391B (en) * | 2022-04-11 | 2023-07-28 | 长沙理工大学 | High-density phosphorylated sodium titanate material, preparation method and application |
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