CN104576076B - Water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material and preparation method thereof - Google Patents
Water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material and preparation method thereof Download PDFInfo
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material and preparation method thereof, the constitutional chemistry formula of the titanium phosphorous oxides negative material is (TiO) xPyOz, wherein, z=x+2.5y, 0<x<3,0<y<3,0<z<12.The present invention have developed novel anode material titanium phosphorous oxides using simple preparation method, the material preparation process is simple, preparation integrally put into it is cheap, it is green, and there is higher specific capacity, apply has good cyclical stability in super capacitance cell.
Description
Technical field
The invention belongs to electrochemical energy technical field, and in particular to a kind of titanium phosphorous oxides negative material, its preparation side
Method and its water base sodium ion hybrid capacitor battery application.
Background technology
High performance lithium ion energy storage system is with its high energy density, the cycle life of high power density and length
As the study hotspot of electrochemical field.However, as lithium-ion energy storage device is gradually applied to electric automobile etc. on a large scale
In energy storage device, the demand of lithium will greatly increase, and the reserves of lithium are very limited amount of, and skewness, and this is for hair
Exhibition may turn into a major issue on a large scale and for the energy storage device of long-life.Therefore, new long-life storage is developed
Energy device is extremely urgent.It is all the sodium ion of periodic table of elements I main group and lithium ion has many similarities, therefore sodium ion
Also it is entirely possible to construct a kind of energy storage device of excellent performance as lithium ion, and sodium has abundant storage in the earth's crust
Amount, accounts for 2.83%, enriches element for the 6th, and widely distributed, and cost is low.If the sodium ion energy storage with excellent service behaviour
Device is developed, and it will possess the competitive advantage bigger than lithium-ion energy storage device, has fairly good application prospect.
The ratio energy of electrochemical capacitor is still than relatively low at present, and the specific power of battery is relatively low, is asked to solve this
Topic, battery and ultracapacitor are used in combination people, during normal work, provided by battery needed for power；Start or need
When wanting high current, then provided by capacitor, on the one hand improve battery cryogenic property it is bad the shortcomings that；Can solve to be used for work(
Rate requires the application scenario of higher pulse current, such as GSM, GPRS.Capacitor and battery, which are used in combination, can extend battery
Life-span, but this will increase battery annex, with current energy device it is short and small it is frivolous wait development disagree.Utilize electrochemistry electricity
The principle of container and battery, exploitation mixed capacitor are hybrid capacitor battery as new energy-storage travelling wave tube, are a kind of Jie
Novel energy-storing element between ultracapacitor and battery, its existing electric double layer capacitance energy storage, there is sodium (lithium) ion deinsertion again
Energy storage, therefore have high-energy-density and high power density concurrently, it is one of large-scale optimal selection of electrical source of power.And electrode material
It is the research emphasis for developing sodium ion hybrid capacitor battery.Ti-based compound has energy density height as negative material,
Undeformed, the electrode cycle stable performance during the insertion of lithium (sodium) ion and abjection, up to tens thousand of times.Ke Sun etc. are reported
With LiMn2O4As positive electrode, titanium salt (TiP2O7) negative material is used as, full battery is assembled in Aqueous Lithium Salts electrolyte
(Journal of Power Sources,2013,09,114).The power density and energy density of the titanium salt material are all relatively low,
Poor circulation, and the material in aqueous can slow mechanism dissolved, it is unstable.A kind of titanyl salt is then used in CN1326594A
As the additive of positive electrode manganese dioxide, alternative titanyl salt includes TiOSO in its Patent4, TiP2O7,
La2Ti4O4(SO4)7, Ti2O1.3(PO4)1.6, Cd2TiNbO6F, PbBi2TiNbO8(OH), CeTi2(O,OH)6, and preferable titanyl
Salt is TiOSO4, when including titanyl salt in cell cathode, mainly extend electricity by changing discharge process and cathode product
The service life in pond, itself does not play substantial role, does not almost have much improvement results to the performance of battery, it is used
Electrolyte be the Sodium Hydroxide Alkaline aqueous solution, environment is polluted.
Therefore, the field can use foul solution as electricity there is an urgent need to a kind of super capacitance cell of excellent performance
Solve liquid.
The content of the invention
It is contemplated that the defects of overcoming existing sodium ion super capacitance cell to exist, the invention provides a kind of water base sodium
Ar ion mixing super capacitance cell titanium phosphorous oxides negative material, its preparation method and its application.
The invention provides a kind of water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material, the titanium
The constitutional chemistry formula of phosphorous oxides negative material is (TiO) xPyOz (z=x+2.5y), wherein 0<x<3,0<y<3,0<z<12.
It is preferred that Ti in the titanium phosphorous oxides negative material：P mol ratio is 1：0.5-3.
Also, present invention also offers a kind of preparation method of the titanium phosphorous oxides negative material, including：
1) by titanium source, phosphate of soluble titanium salt be respectively phosphorus source, to containing titanium source, phosphorus source solution in add alkalescence
Precipitating reagent, and solution described in 60-80 DEG C of heating water bath until solvent be evaporated completely, obtain the first presoma；
2) after the first presoma washing prepared step 1), dried at 50-120 DEG C, obtain the second presoma；
3) the second presoma prepared by step 2) is calcined at 600-900 DEG C, obtains the titanium phosphorous oxides negative pole material
Material.
It is preferred that the titanium source includes TiCl4、TiBr4、Ti(SO4)2、C16H36O4At least one of Ti, phosphorus source
Including NaH2PO4、Na2HPO4、NH4H2PO4、(NH4)2HPO4At least one of.
It is preferred that titanium and the phosphorus mol ratio in phosphorus source are 1 in titanium source：(1-2).
It is preferred that containing titanium source, phosphorus source solution in solvent include water, ethanol, at least one of PEG-400.
It is preferred that alkaline precipitating agent includes at least one of ammoniacal liquor, sodium carbonate, sodium acetate.
It is preferred that the heat time is 2-10 hours in step 1)；Drying time is 4-12 hours in step 2)；Step 3)
In, the heating rate of roasting is 1-10 DEG C/min, roasting time 2-12 hours.
In addition, present invention also offers a kind of super capacitance cell for including above-mentioned titanium phosphorous oxides negative material, it is described
In super capacitance cell the composition of negative pole include 75-85wt% titanium phosphorous oxides negative material, 10-20wt% conductive agent,
And 5% binding agent.
Beneficial effects of the present invention：
The present invention discloses a kind of preparation method of water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material,
By the use of simple Co deposited synthesis, a kind of new titanium phosphorous oxides ((TiO) xPyOz) is super as the mixing of water system sodium ion
Level capacitance cell negative electrode material, material overall structure is stable, abundant raw material, meanwhile, technique is simple, prepares the price integrally put into
It is cheap, its security and the feature of environmental protection are not substantially increased using any poisonous or generation noxious material in process of production, and
Can simultaneously utilize two electrodes capacitance characteristic and battery behavior, can significantly improve the capacitor batteries system energy density and
Power density, apply has good cyclical stability in hybrid super capacitor batteries, and usage time, can be up to more than 10 years
Worked within the scope of wider temperature, each monomer can realize high consistency.
Brief description of the drawings
Fig. 1 is the XRD of (TiO) the xPyOz samples prepared in one embodiment of the present invention；
Fig. 2 is the SEM spectrum that (TiO) xPyOz samples are prepared in the embodiment of the present invention 1；
Fig. 3 is that (TiO) the xPyOz samples prepared in an embodiment of the invention are assembled into hybrid super with activated carbon
The cycle performance curve of the constant current charge-discharge of capacitor batteries.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that accompanying drawing and following embodiments
The present invention is merely to illustrate, is not intended to limit the present invention.
To realize the technical purpose of the present invention, reach above-mentioned technique effect, present invention firstly provides a kind of coprecipitation
Synthesize the method for titanium phosphorous oxides material and its application in water base sodium ion hybrid capacitor battery.The present invention is using simple
Preparation method have developed novel anode material titanium phosphorous oxides, the material preparation process is simple, prepares the valency that integrally puts into
Lattice are cheap, green, and have higher specific capacity, and apply has good cyclical stability in super capacitance cell,
Under suitable both positive and negative polarity proportioning, the hybrid capacitor battery shows higher energy density and excellent cycle performance, because
This material has good application prospect in water system sodium ion mixing capacitor batteries.
The invention provides a kind of sodium ion hybrid capacitor battery, including positive plate, negative plate, electrolyte, barrier film
And shell, active material on the positive plate is the activated carbon of the loose structure of bigger serface, the work on the negative plate
Property material is titanium phosphorus oxidation composition material ((TiO) xPyOz).
It is negative with titanium phosphorous oxides ((TiO) xPyOz) the invention provides a kind of water system sodium ion hybrid capacitor battery
The preparation method of pole material, the titanium phosphorous oxides material are by using Co deposited synthesis, are formed as (TiO) xPyOz, institute
The method of stating includes：
1) Co deposited synthesis presoma (TiO) xPyOz is utilized, wherein 0<x<3,0<y<3,0<z<12；
2) required product can be obtained by being calcined the presoma (TiO) xPyOz at high temperature.
Active material on the negative plate uses the titanium phosphorous oxides ((TiO) xPyOz) of Co deposited synthesis, including with
Lower step：
(a) using soluble titanium salt as titanium source, phosphate is phosphorus source, by Ti：P mol ratio is 1：1-2 ratio is matched somebody with somebody
Material, titanium source, phosphorus source are weighed as mixed material, and by mixed material mixed dissolution, then adds a certain amount of precipitating reagent weak base
(such as ammoniacal liquor, sodium carbonate, sodium acetate etc.), in 60-80 DEG C of heating water bath 8h, untill solvent is evaporated completely；
(b) gained presoma in step (a) is washed with solvent, the dissolving of some soluble-salts is washed off, then 50~
4~12h is dried in 120 DEG C of baking ovens, obtains presoma；
(c) presoma of gained in step (b) is placed in Muffle furnace and is warming up to 600~900 DEG C with 2 DEG C/min speed
2~12h is calcined, cooling, obtains (TiO) xPyOz.
The titanium source can be TiCl4, TiBr4, Ti (SO4)2, C16H36O4At least one of Ti, phosphorus source can be
NaH2PO4, Na2HPO4, NH4H2PO4, (NH4)2HPO4At least one of.
Solvent can be distilled water in the step (b), ethanol, at least one of PEG-400.
The positive plate and negative plate are using foamed nickel current collector.
The positive plate is by the activated carbon that mass percent is 85%, 10% conductive agent and 5% binding agent composition.
Conductive agent and 5% of the negative plate by mass percent for 75%-85% (TiO) xPyOz, 10%-20%
Binding agent composition.
The mass ratio of the active material on active material and negative plate on the positive plate is 1:1-3.Wherein it is preferably
1:2。
The making step of negative plate of the present invention is as follows：
A, the pretreatment of foamed nickel current collector：Nickel foam is first placed in sonic oscillation 5-20min in acetone, is then placed in again
Sonic oscillation 1-12h in alcohol, remove the grieshoch in nickel screen and the impurity such as greasy dirt on surface, after it is flattened on a hydraulic press,
Pressure is 10-30MPa；
B, by mass percentage (TiO) xPyOz for 75%~85%, 10%~20% conductive agent and 5% bonding
Agent, pasty state is stirred into together with solvent, solvent is water or ethanol, and it is uniformly then coated in into pretreated nickel foam
On, after being dried in 80 DEG C of baking ovens, dried pole piece is compressed on a hydraulic press, then be placed in 120 DEG C of vacuum drying chambers, pass through
Cathode pole piece is obtained after vacuum drying at least 12h.
The making step of positive plate of the present invention is as follows：Mass percent be 85% activated carbon, 10% conductive agent and 5%
Binding agent pasty state is stirred into together with solvent, solvent is water or ethanol, and it is uniformly then coated in into pretreated bubble
On foam nickel, after being dried in 65 DEG C of baking ovens, dried pole piece is compressed on a hydraulic press, then be placed in 100 DEG C of vacuum drying chambers
In, obtain anode pole piece after vacuum dried at least 12h.
The electrolyte is 1M Na2SO4The aqueous solution.
The barrier film is porous celgard 3501, and the thickness of the porous barrier films of celgard 3501 is 15-50 μm, hole
Gap rate is 35-55%, and pore size is 0.05-0.2 μm.
The barrier film is the ultra-fine cotton porous septum of battery, and porosity 35-55%, pore size is 0.05-0.2 μm.
The shell is lead-acid accumulator plastic casing.
The sodium ion hybrid capacitor battery by positive plate, negative plate, the barrier film between positive/negative plate, have from
Neutral aqueous solution electrolyte and the shell composition of subconductivity, positive active material used are the porous knot of bigger serface
The activated carbon of structure, positive plate is by the activated carbon that mass percent is 85%, 10% conductive agent and 5% binding agent composition；Institute
The negative electrode active material stated is a kind of titanium phosphorous oxides ((TiO) xPyOz), and negative plate is 75%~85% by mass percent
(TiO) xPyOz, 10%~20% conductive agent and 5% binding agent composition.Described positive plate and negative plate are using bubble
Foam nickel set fluid.Electrolyte is 1MNa2SO4The aqueous solution, barrier film use porous celgard3501 or battery super glass wool
Porous septum, composition mixing capacitor batteries.In charge and discharge process, can make full use of titanium phosphorous oxides ((TiO) xPyOz) and
The surface texture properties of absorbent charcoal material, electric double layer capacitance is formed in the electrolytic solution and improves the energy storage capacity of battery and is advantageous to improve
Power density.Because of its excellent chemical property, relatively low voltage platform, the operating voltage of battery can be significantly improved, so as to
Improve the energy storage density of battery.
The present invention discloses a kind of preparation method of water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material,
By the use of simple Co deposited synthesis, a kind of new titanium phosphorous oxides ((TiO) xPyOz) is super as the mixing of water system sodium ion
Level capacitance cell negative electrode material, material overall structure is stable, abundant raw material, meanwhile, technique is simple, prepares the price integrally put into
It is cheap, its security and the feature of environmental protection are not substantially increased using any poisonous or generation noxious material in process of production, and
Can simultaneously utilize two electrodes capacitance characteristic and battery behavior, can significantly improve the capacitor batteries system energy density and
Power density, apply has good cyclical stability in hybrid super capacitor batteries, and usage time, can be up to more than 10 years
Worked within the scope of wider temperature, each monomer can realize high consistency.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to is interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
(1) preparation of (TiO) xPyOz negative poles
With C16H36O4Ti is titanium source, (NH4)2HPO4For phosphorus source, by Ti：P mol ratio is 1：1 ratio carries out dispensing, claims
Titanium source, phosphorus source are measured as mixed material, and by mixed material mixed dissolution, a certain amount of aqueous sodium carbonate is added, at 80 DEG C
Heating water bath 8h, untill solvent is evaporated completely；Gained presoma is washed with solvent, the dissolving of some soluble-salts is washed off,
Then 12h is dried in 100 DEG C of baking ovens, obtains presoma；It is subsequently placed in Muffle furnace and is warming up to 900 with 2 DEG C/min speed
DEG C roasting 5h, cooling, obtain (TiO) xPyOz negative materials, its XRD is as shown in figure 1, SEM is as shown in Figure 2.
(2) preparation of both positive and negative polarity pole piece
It is 80 in mass ratio by (TiO) the xPyOz samples synthesized, conductive agent, polyfluortetraethylene of binding element (PTFE):
15:5 is well mixed, is configured to slurry and is coated uniformly in nickel foam.Dry, rolling.12h in vacuum drying chamber is placed in again, is obtained
To (TiO) xPyOz pole pieces.Activated carbon is that commercial activated carbon, conductive agent and binding agent and above-mentioned conductive agent binder phase are same, system
Standby slurry, is matched according to activated carbon：Conductive agent：Binding agent is 85:10:5 slurries, are evenly coated in foamed nickel current collector, equally
Activated carbon pole piece is prepared according to the method described above.
(3) assembling and test of (TiO) xPyOz/AC system hybrid capacitor batteries
Positive electrode uses activated carbon (production of Henan factory), and negative material uses (TiO) xPyOz, by both electrodes
Pairing is assembled into hybrid capacitor battery, and the mass ratio for controlling both positive and negative polarity active material is 1:1, using porous celgard
3501 are used as barrier film, 1mol/LNa2SO4The aqueous solution is assembled into (TiO) xPyOz/AC system hybrid capacitors as electrolyte
Battery.Constant current charge-discharge test is carried out on blue electricity, discharge and recharge section is 0 to 1.8V, and its charging and discharging curve is as shown in Figure 3.
First discharge specific capacity is 46.0mAh/g, as 92F/g under 100mA/g current densities, and capacity is kept after 1000 circulations
88.7%.Such as Fig. 3.
Embodiment 2
(1) preparation of (TiO) xPyOz negative poles
With Ti (SO4)2For titanium source, (NH4)2HPO4For phosphorus source, by Ti：P mol ratio is 1：1.5 ratio carries out dispensing,
Titanium source, phosphorus source are weighed as mixed material, and by mixed material mixed dissolution, a certain amount of ammoniacal liquor is added, adds in 60 DEG C of water-baths
Hot 8h, untill solvent is evaporated completely；Gained presoma is washed with solvent, the dissolving of some soluble-salts washed off, Ran Hou
10h is dried in 120 DEG C of baking ovens, obtains presoma；It is subsequently placed in Muffle furnace and 800 DEG C of roastings 2 is warming up to 2 DEG C/min speed
~12h, cooling, obtains (TiO) xPyOz negative materials.
(2) preparation of pole piece, the assembling of super capacitance cell and the test of chemical property are tested with embodiment 1.It will close
It is negative pole into (TiO) xPyOz gone out, makes negative plate according to the method described above, anode activated charcoal uses commercial activated carbon, equally pressed
Activated carbon positive plate is prepared according to the above method.Both electrode pairs are then assembled into hybrid capacitor battery, controlled
The mass ratio of both positive and negative polarity active material is 1:2, with embodiment 1, discharge and recharge section is 0 to 1.8V for barrier film, electrolyte.In 100mA/
Under g current density, specific discharge capacity 68.4mAh/g, as 121F/g.After 5000 circulations, capacity is kept
81.5%.
Embodiment 3
(1) preparation of (TiO) xPyOz negative poles
With TiCl4For titanium source, (NH4)2HPO4For phosphorus source, by Ti：P mol ratio is 1：2 ratio carries out dispensing, weighs
Titanium source, phosphorus source add a certain amount of aqueous sodium carbonate, in 70 DEG C of water as mixed material, and by mixed material mixed dissolution
Bath heating 8h, untill solvent is evaporated completely；Gained presoma is washed with solvent, the dissolving of some soluble-salts washed off, so
12h is dried in 80 DEG C of baking ovens afterwards, obtains presoma；It is subsequently placed in Muffle furnace and 700 DEG C of roastings is warming up to 2 DEG C/min speed
8h is burnt, cooling, obtains (TiO) xPyOz negative materials.
(2) preparation of pole piece, the assembling of super capacitance cell and the test of chemical property are tested with embodiment 1.It will close
It is negative pole into (TiO) xPyOz gone out, makes negative plate according to the method described above, positive electrode active materials uses commercial activated carbon, equally
Activated carbon positive plate is prepared according to the method described above.Both electrode pairs are then assembled into hybrid capacitor battery, controlled
The mass ratio of both positive and negative polarity active material processed is 1:2, with embodiment 1, discharge and recharge section is 0 to 1.8V for barrier film, electrolyte.
Under 100mA/g current density, specific discharge capacity 43.6mAh/g, as 89.9mAh/g, after 3000 circulations, hold
Amount keeps 86.5%.
Embodiment 4
(1) preparation of (TiO) xPyOz negative poles
With TiCl4For titanium source, (NH4)2HPO4For phosphorus source, by Ti：P mol ratio is 1：2 ratio carries out dispensing, weighs
Titanium source, phosphorus source add a certain amount of aqueous sodium acetate solution, in 60 DEG C of water as mixed material, and by mixed material mixed dissolution
Bath heating 8h, untill solvent is evaporated completely；Gained presoma is washed with solvent, the dissolving of some soluble-salts washed off, so
12h is dried in 120 DEG C of baking ovens afterwards, obtains presoma；It is subsequently placed in Muffle furnace and is warming up to 600 DEG C with 2 DEG C/min speed
12h is calcined, cooling, obtains (TiO) xPyOz negative materials.
(2) preparation of pole piece, the assembling of super capacitance cell and the test of chemical property are tested with embodiment 1.It will close
It is negative pole into (TiO) xPyOz gone out, makes negative plate according to the method described above, positive electrode active materials uses commercial activated carbon, equally
Activated carbon positive plate is prepared according to the method described above.Both electrode pairs are then assembled into hybrid super capacitor, controlled
The mass ratio of both positive and negative polarity active material is 1:3, with embodiment 1, discharge and recharge section is 0 to 1.8V for barrier film, electrolyte.In 100mA/
Under g current density, specific capacity 39.6mAh/g, i.e. 78.9F/g.After 5000 circulations, capacity keeps 83.7%.
Titanium phosphorous oxides of the present invention is used as water system sodium ion hybrid capacitor cell negative electrode material first, and makes
Standby technique is simple and convenient to operate, and security reliability is high, and cost is low, has universality, electrochemical performance.
Claims (8)
- A kind of 1. water base sodium ion hybrid capacitor battery titanium phosphorous oxides negative material, it is characterised in that the titanium phosphorus The constitutional chemistry formula of oxide cathode material is (TiO) xPyOz, wherein, z=x+2.5y, 0<x<3,0<y<3,0<z<12, it is described Titanium phosphorous oxides negative material is prepared via a method which：1）Be respectively phosphorus source by titanium source, phosphate of soluble titanium salt, to containing titanium source, phosphorus source solution in add alkaline sedimentation Agent, and solution described in 60-80 DEG C of heating water bath until solvent be evaporated completely, obtain the first presoma；2）By step 1）After the first presoma washing prepared, dried at 50-120 DEG C, obtain the second presoma；3）By step 2）The second presoma prepared is calcined at 600-900 DEG C, obtains the titanium phosphorous oxides negative material.
- 2. titanium phosphorous oxides negative material according to claim 1, it is characterised in that the titanium phosphorous oxides negative material Middle Ti：P mol ratio is 1：0.5-3.
- 3. titanium phosphorous oxides negative material according to claim 1, it is characterised in that the titanium source includes TiCl4、 TiBr4、Ti(SO4)2、C16H36O4At least one of Ti, phosphorus source include NaH2PO4、Na2HPO4、NH4H2PO4、（NH4）2HPO4At least one of.
- 4. titanium phosphorous oxides negative material according to claim 1, it is characterised in that titanium rubs with the phosphorus in phosphorus source in titanium source You are than being 1：（1-2）.
- 5. titanium phosphorous oxides negative material according to claim 1, it is characterised in that containing titanium source, phosphorus source solution in Solvent includes at least one of water, ethanol, PEG-400.
- 6. titanium phosphorous oxides negative material according to claim 1, it is characterised in that alkaline precipitating agent includes ammoniacal liquor, carbon At least one of sour sodium, sodium acetate.
- 7. titanium phosphorous oxides negative material according to claim 1, it is characterised in that step 1）The middle heat time is 2-10 Hour；Step 2）Middle drying time is 4-12 hours；Step 3）In, the heating rate of roasting is 1-10 DEG C/min, roasting time 2-12 hours.
- 8. a kind of super capacitance cell for including titanium phosphorous oxides negative material any one of claim 1 to 7, its feature It is, the composition of negative pole includes 75-85wt% titanium phosphorous oxides negative material, 10-20wt% in the super capacitance cell Conductive agent and 5% binding agent.
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