CN105185978A - Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof - Google Patents

Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof Download PDF

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Publication number
CN105185978A
CN105185978A CN201410280131.XA CN201410280131A CN105185978A CN 105185978 A CN105185978 A CN 105185978A CN 201410280131 A CN201410280131 A CN 201410280131A CN 105185978 A CN105185978 A CN 105185978A
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manganese
oxygen compound
battery
aqueous solution
sodium ion
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胡勇胜
王跃生
陈立泉
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Institute of Physics of CAS
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Institute of Physics of CAS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a manganese-containing oxygen compound used as a negative active substance. The general formula of the manganese-containing oxygen compound is Nax[Mn(1-y)Ay]O2-z, wherein x is not smaller than 0.2 and not greater than 0.7, y is not smaller than 0 and not greater than 1.15-x, z is not smaller than -0.02 and not greater than 0.02, and A is one or more selected from B, Ti, Fe, V, Co and Cr elements. The manganese-containing oxygen compound can be used as a negative active substance of an aqueous solution sodion secondary battery, and the negative active substance has appropriate potential, has higher capacity than active carbon, and has the advantages of low cost of a raw material, cycle stability and high compact density.

Description

As negative electrode active material containing manganese and oxygen compound and its production and use
Technical field
The present invention relates to cell art.Particularly, the present invention relates to aqueous solution sodium ion secondary battery technical field, in particular to a kind of be used as aqueous solution sodium ion secondary battery negative electrode active material containing manganese and oxygen compound and preparation method thereof, and the aqueous solution sodium ion secondary battery negative pole containing this compound and the aqueous solution sodium ion secondary battery containing this negative pole.
Background technology
Along with the development of the regenerative resources such as the continuous consumption of traditional energy and wind energy/solar energy, energy storage becomes one of key technology of restriction regenerative resource large-scale application.In all energy storage systems, electrochemical energy storage is to safeguard the extensive concern simple, conversion efficiency is high, flexibility advantages of higher obtains national governments.In electrochemical energy storage, lithium ion battery is used widely in people's life with its high voltage, long circulation life.High energy density, powerful application apparatus is applied to from little household electrical appliance, such as, power vehicle and national grid.But due to the limited and skewness of lithium resource reserves, along with the consumption gradually of limited lithium resource, the cost of lithium raises gradually, is restricted as scale energy storage lithium ion battery.Sodium is as the alkali metal close with lithium chemistry, and have the advantages such as rich reserves, the cost of raw material be low, the research of room temperature sodium-ion battery obtains the concern of more and more people.
The operation principle basic simlarity of sodium-ion battery and lithium ion battery, in the sodium-ion battery of non-water, electrolyte is made by sodium hexafluoro phosphate or sodium perchlorate being dissolved in organic solution agent, but because organic solvent is volatile, molten boiling point is lower, inflammable, explosive, and easily there are some safety problems.From security performance and become originally, aqueous solution sodium ion secondary battery receives extensive concern.Existing aqueous solution sodium ion secondary battery positive electrode mainly concentrates on Na 0.44mnO 2, NaMnO 2and some Prussian blue compounds, negative pole mainly contains active carbon and titanium phosphate sodium (NaTi 2(PO 4) 3), wherein active carbon specific capacity is lower, compacted density is low, material cost is high; For titanium phosphate sodium, due to Na +with H 3o +may exchange, cycle life is short, so the negative material of aqueous solution sodium ion secondary battery receives challenge.
The manganese resource reserves of China are large, aboundresources, but the compound of manganese have not been reported as the application in aqueous solution sodium ion secondary battery negative electrode active material.
Summary of the invention
For overcoming the shortcomings such as aqueous solution sodium ion secondary battery negative electrode active material is single, the cost of raw material is high, compacted density is low in prior art, the invention provides a kind of can be used as aqueous solution sodium ion secondary battery negative electrode active material containing manganese and oxygen compound and its production and use.On the other hand, present invention also offers the aqueous solution sodium ion secondary battery negative pole containing this manganese and oxygen compound and the aqueous solution sodium ion secondary battery containing this negative pole.
Above-mentioned purpose of the present invention is achieved by the following technical solution:
On the one hand, the invention provides a kind of be used as aqueous solution sodium ion secondary battery negative electrode active material containing manganese and oxygen compound, should be containing general formula of manganese and oxygen compound: Na x[Mn (1-y)a y] O 2-z, wherein, 0.2≤x≤0.7,0≤y≤1.15-x and-0.02≤z≤0.02; Wherein, A is selected from one or more in B, Ti, Fe, V, Co, Al and Cr element.
In some embodiments, in described general formula, 0.3≤x≤0.55,0≤y≤1.15-x and-0.01≤z≤0.01.In some embodiments, 0.3≤x≤0.5,0≤y≤1.1-x and-0.01≤z≤0.01.In preferred embodiments, x=0.44,0≤y≤1-x and-0.01≤z≤0.01.
In some embodiments, A is selected from one or more in Ti, Fe, V and Cr element.
On the other hand, the invention provides and a kind ofly prepare the above-mentioned method containing manganese and oxygen compound, described method is solid phase method or sol-gel process.
In some embodiments, described solid phase method comprises the following steps:
(1) by Na:Mn:A=(1.00 ~ 1.05) x:(1-y): the amount of substance of y, than the oxide of weighing sodium carbonate, manganese sesquioxide managnic oxide and A, obtains precursor powder after ground and mixed;
(2) precursor powder that step (1) obtains is processed 8 ~ 25 hours at 650 ~ 1000 DEG C, obtain described containing manganese and oxygen compound.
In preferred embodiments, precursor powder described in step (2) processes at the temperature of 800 ~ 1000 DEG C.In some embodiments, the time of process is 12 ~ 24 hours.
In some preferred embodiments, the oxide of described A comprises TiO 2, Fe 2o 3, Cr 2o 3and V 2o 3.
In some embodiments, described sol-gel process comprises the following steps:
(1 ') is by Na:Mn:A=x:(1-y): the amount of substance of y is than taking sodium acetate, Mn nitrate and the salt containing A, be dissolved in absolute ethyl alcohol respectively, add complexing agent after mixing, heat 5 ~ 8 hours at 50 ~ 80 DEG C, obtain aqueous precursor gel;
The aqueous precursor gel that step (1 ') obtains by (2 ') preliminary treatment 2 ~ 6 hours at 250 ~ 600 DEG C, then 8 ~ 20 hours are processed at 750 ~ 1000 DEG C, obtain described containing manganese and oxygen compound.
In some preferred embodiments, described complexing agent is citric acid.
Again on the one hand, the invention provides a kind of negative pole for aqueous solution sodium ion secondary battery, described negative pole comprises conductive additive, binding agent, collector and above-mentioned containing manganese and oxygen compound.
In some embodiments, described conductive additive is selected from one or more in active carbon, five nickel lanthanums, carbon black, acetylene black, graphite powder, carbon nano-tube and Graphene.
In some embodiments, described binding agent is polytetrafluoroethylene or Kynoar.
In some embodiments, described collector is nickel screen, titanium net, stainless (steel) wire, graphite felt or graphite cake.
It should be noted that the present invention not by the restriction of negative pole preparation method.Should be appreciated that the method preparing negative pole conventional in this area all can be used for the present invention.Such as, the method preparing negative pole can be: by of the present invention containing manganese and oxygen compound and the conductive additive ground and mixed accounting for total weight 0 ~ 50%, preferably, before ground and mixed, conducting polymer such as polyaniline can also be adopted, polypyrrole or 3, one or more in 4-ethylenedioxy thiophene carry out coated to described compound, and then carry out film-making with binding agent, the thickness of the electrode slice of preparation can be 2 ~ 1000 μm, the electrode obtained sheet is cut into applicable shape (such as square or circular), dry at 70 ~ 120 DEG C in the environment of vacuum again, obtain.
Another aspect, the invention provides a kind of aqueous solution sodium ion secondary battery, and described secondary cell comprises the above-mentioned negative pole for aqueous solution sodium ion secondary battery.
In some embodiments, the described aqueous solution sodium ion secondary battery alkaline electrolyte that also comprises positive pole and be placed between described positive pole and described negative pole.
The present invention, also not by the restriction of aqueous solution sodium ion secondary battery preparation method, can adopt known method to prepare the aqueous solution sodium ion secondary battery comprising the parts such as negative pole of the present invention, conventional positive pole and alkaline electrolyte.Such as, the method preparing CR2032 button cell can be adopted to prepare aqueous solution sodium ion secondary battery of the present invention.
Present invention also offers above-mentioned containing the purposes of manganese and oxygen compound as aqueous solution sodium ion secondary battery negative electrode active material.
Aqueous solution sodium ion secondary battery of the present invention has that cost is low, the advantage such as have extended cycle life, the fields such as the energy storage device needed for solar energy or wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station can be widely used in, especially be suitable as the extensive energy storage device needed for solar energy or wind power generation.
The present inventor is by finding after a large amount of experiments, of the present invention have tunnel structure (space group is Pbam) containing manganese and oxygen compound, its crystal structure is stablized, hydrone or proton can not be embedded in tunnel structure, can used as the negative electrode active material of aqueous solution sodium ion secondary battery, and show unexpected good security performance, high coulombic efficiency and compacted density, and low cost.Adopt the present invention containing negative electrode active material voltage range 1.8 ~ 2.8VvsNa in nonaqueous electrolytic solution of manganese and oxygen compound +between/Na, average potential at 2.3V, cycle efficieny more than 99.5% weekly; In the battery of the aqueous solution, reference electrode is that in the half-cell of calomel, voltage range is about-0.6 ~ 0V, stable circulation, and the 100 weeks capability retentions that circulate can reach more than 99%.This illustrates, the compounds of this invention has applicable potential range, storage sodium capacity and capability retention as negative electrode active material.
Compared with prior art, the present invention at least has following beneficial effect: under adopting negative electrode active material of the present invention to have suitable current potential, identical multiplying power, capacity is higher than active carbon, and the cost of raw material is cheap, stable circulation, compacted density are high.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 shows X-ray diffraction (XRD) collection of illustrative plates containing manganese and oxygen compound of the embodiment of the present invention 1;
Fig. 2 shows the space structure figure containing manganese and oxygen compound of the embodiment of the present invention 1;
Fig. 3 shows the scanning electron microscope (SEM) photograph (SEM) containing manganese and oxygen compound of the embodiment of the present invention 1;
Fig. 4 shows the head week charging and discharging curve of the non-aqueous solution sodium ion secondary battery negative electrode active material of the embodiment of the present invention 1;
Fig. 5 shows the cyclic curve of the non-aqueous solution sodium ion secondary battery negative electrode active material of the embodiment of the present invention 1;
Fig. 6 shows the charging and discharging curve of the non-aqueous solution sodium ion secondary battery negative electrode active material of embodiment 2;
Fig. 7 shows the charging and discharging curve of the non-aqueous solution sodium ion secondary battery negative electrode active material of embodiment 3;
Fig. 8 shows the charging and discharging curve of the non-aqueous solution sodium ion secondary battery negative electrode active material of embodiment 4;
Fig. 9 shows the charging and discharging curve of the non-aqueous solution sodium ion secondary battery negative electrode active material of embodiment 5;
Figure 10 shows the full battery charging and discharging curve of aqueous solution sodium ion secondary battery of embodiment 6;
Figure 11 illustrates the charging and discharging curve of the aqueous solution sodium ion secondary battery half-cell of embodiment 7;
Figure 12 illustrates the cyclic curve of the aqueous solution sodium ion secondary battery half-cell of embodiment 7;
Figure 13 illustrates the charging and discharging curve of the aqueous solution sodium ion secondary battery half-cell of embodiment 8;
Figure 14 illustrates the cyclic curve of the aqueous solution sodium-ion battery secondary cell of embodiment 8;
Figure 15 shows the first all charging and discharging curves of active carbon of comparative example 11;
Figure 16 shows the cyclic curve of the active carbon of comparative example 11.
Embodiment
The present invention is further illustrated below by specific embodiment, but, should be understood to the use that these embodiments are only used for specifically describing more in detail, and should not be construed as limiting the present invention in any form.
General description is carried out to the material used in the present invention's test and test method in this part.Although for realizing many materials that the object of the invention uses and method of operation is well known in the art, the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and method of operation are well known in the art.
embodiment 1
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.44mn 0.44ti 0.56o 2, concrete steps are:
(1) analytically pure Na is taken by the amount of substance ratio of Na:Mn:Ti=0.44:0.44:0.56 2cO 3, Mn 2o 3and TiO 2, mixing, ground and mixed half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours at 950 DEG C, gained brownish black material is of the present invention containing manganese and oxygen compound Na 0.44mn 0.44ti 0.56o 2, the density of material is 2.6g/cm 3, its XRD collection of illustrative plates, space structure figure and scanning electron microscope (SEM) photograph are shown in Fig. 1 to Fig. 3 respectively.
What obtained by the present embodiment contains the negative pole making non-aqueous solution sodium ion secondary battery after manganese and oxygen compound grinds, and concrete steps comprise: by Na 0.44mn 0.44ti 0.56o 2powder mixes according to the mass ratio of 75:20:5 with acetylene black and binding agent Kynoar (PVDF), add appropriate nmp solution, in the environment of air drying, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, the pole piece of 8 × 8mm is cut into after drying, at 100 DEG C dry 10 hours under vacuum, be transferred to glove box immediately for subsequent use.
Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal sheet as to electrode, the NaClO of 1M 4/ EC:DEC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to test, discharging by voltage is 1.8V, and charging by voltage is 2.8V, and all tests are all carried out under C/5 current density.Test result is shown in Fig. 4, and cyclic curve is shown in Fig. 5.Wherein, Fig. 4 is the head week charging and discharging curve in non-aqueous solution, and first all efficiency is 97%, and specific discharge capacity is 52 MAhs/g.In Fig. 5, first half be C/5 circulation, after for 1C circulate, as can be seen from Figure 5,1C circulation volume still has 32 MAhs/g, stable circulation.
embodiment 2
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.44mn 0.83ti 0.17o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Ti=0.45:0.83:0.17 2cO 3, Mn 2o 3and TiO 2, mixing, in agate jar, 350 revs/min of mixing 4 hours of dry grinding, obtain precursor powder;
(2) precursor powder step (1) obtained, at the tableting under pressure of 18MPa, then transfers to Al 2o 3in crucible, heat treatment 12 hours in air atmosphere, at 950 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 0.83ti 0.17o 2.
What obtained by the present embodiment makes non-aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 1, and carries out electro-chemical test, and method of testing is with embodiment 1.Test voltage scope is 1.8V ~ 2.8V, and test multiplying power is C/5, and test result is shown in Fig. 6.As can be seen from Figure 6, first all specific discharge capacities are 52 MAhs/g, and charge specific capacity is 45.2 MAhs/g.
embodiment 3
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.44mn 078ti 0.22o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Ti=0.46:0.78:0.22 2cO 3, Mn 2o 3and TiO 2, mixing, in agate jar, 400 revs/min of mixing 4 hours of dry grinding, obtain precursor powder;
(2) precursor powder step (1) obtained, at the tableting under pressure of 20MPa, then transfers to Al 2o 3in crucible, heat treatment 14 hours in air atmosphere, at 950 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 078ti 0.22o 2.
What obtained by the present embodiment makes non-aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 1, and carries out electro-chemical test, and method of testing is with embodiment 1.Test voltage scope is 1.8V ~ 2.8V, and test multiplying power is C/5, and test result is shown in Fig. 7.As can be seen from Figure 7, first all specific discharge capacities are 53 MAhs/g, and charge specific capacity is 46 MAhs/g.
embodiment 4
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.44mn 0.66ti 0.34o 1.99, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Ti=0.455:0.66:0.34 2cO 3, Mn 2o 3and TiO 2, mixing, in agate jar, 300 revs/min of mixing 4 hours of dry grinding, obtain the precursor powder of black;
(2) precursor powder step (1) obtained, at the tableting under pressure of 20MPa, then transfers to Al 2o 3in crucible, heat treatment 18 hours in air atmosphere, at 950 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 0.66ti 0.34o 1.99.
What obtained by the present embodiment makes non-aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 1, and carries out electro-chemical test, and method of testing is with embodiment 1.Test voltage scope is 1.8V ~ 2.8V, and test multiplying power is C/5, and test result is shown in Fig. 8.As can be seen from Figure 8, first all specific discharge capacities are 50.4 MAhs/g, and charge specific capacity is 44 MAhs/g.
embodiment 5
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.44mn 0.61ti 0.39o 2, concrete steps are:
(1) Na is taken by the ratio of the amount of substance of Na:Mn:Ti=0.45:0.61:0.39 2cO 3, Mn 2o 3and TiO 2, mixing, in agate jar, 500 revs/min of mixing 4 hours of dry grinding, obtain precursor powder;
(2) precursor powder step (1) obtained, at the tableting under pressure of 20MPa, then transfers to Al 2o 3in crucible, heat treatment 15 hours in air atmosphere, at 900 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 0.61ti 0.39o 2.
What obtained by the present embodiment makes non-aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 1, and carries out electro-chemical test, and method of testing is with embodiment 1.Test voltage scope is 1.8V ~ 2.8V, and test multiplying power is C/5, and test result is shown in Fig. 9.As can be seen from Figure 9, first all specific discharge capacities are 51 MAhs/g, and charge specific capacity is 49.5 MAhs/g.
embodiment 6
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.44mnO 2.Concrete steps are:
(1) sodium acetate (CH is taken by the amount of substance ratio of Na:Mn=0.44:1 3and Mn nitrate (Mn (NO COONa) 3) 2), be dissolved in absolute ethyl alcohol respectively, mix and add with the mol ratio of Na be the citric acid of 10% as complexing agent, at 60 DEG C heat 8 hours, formed aqueous precursor gel;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 6 hours at 300 DEG C in Muffle furnace, then 20 hours are processed at 850 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mnO 2.
Obtained for the present embodiment is mixed according to the mass ratio of 80:10:10 with active carbon and polyfluortetraethylene of binding element (PTFE) containing after manganese and oxygen compound grinding, grind in mortar, then compressing tablet, the sheet rolled is cut into the pole piece of 8 × 8mm, under vacuum in 100 DEG C of dryings 10 hours, save backup.
The assembling of simulated battery is carried out in atmosphere, as to electrode while of material of the present invention, to the Na of 2M 2sO 4add in the aqueous solution a small amount of NaOH be mixed with pH value be the solution of 13 as electrolyte, using glass fibre as barrier film, be assembled into simulated battery.Carry out electro-chemical test, voltage range is 0 ~ 1.6V, and test under the multiplying power of 2C, test result is shown in Figure 10.As can be seen from Figure 10, under the multiplying power of 2C, first all charging capacitys can reach 27.5 MAhs/g, and first all discharge capacities can reach 26.4 MAhs/g.
embodiment 7
What the present embodiment adopted embodiment 6 to prepare contains manganese and oxygen compound Na 0.44mnO 2for active material, assembling aqueous solution sodium-ion battery, concrete steps are as follows:
(1) active material, active carbon and PTFE are rolled sheet according to the mass ratio grinding of 8:1.5:0.5 and prepare electrode material;
(2) be placed on nickel screen by the electrode material of preparation, in the pressure system 1 ~ 10 minute of 5 ~ 25Mpa, obtained electrode is for subsequent use;
(3) taking calomel electrode as reference electrode, is to electrode with platinum electrode, and the electrode obtained with step (2), for work electrode, with the NaOH aqueous solution of pH=13.5 for electrolyte, prepares battery.
Battery is in-0.6 ~ 0V work, and with the rate charge-discharge of 2C, result as shown in FIG. 11 and 12.As can be seen from Figure 11, first all specific discharge capacities are 37.9 MAhs/g, and charge specific capacity is 37.4 MAhs/g, as can be seen from Figure 12, battery after circulation 150 weeks capability retention 94%.
embodiment 8
What the present embodiment adopted embodiment 1 to prepare contains manganese and oxygen compound Na 0.44mn 0.44ti 0.56o 2for active material, assembling aqueous solution sodium-ion battery, concrete steps are as follows:
(1) active material, active carbon and PTFE are rolled sheet according to the mass ratio grinding of 8:1.5:0.5 and prepare electrode material;
(2) be placed on nickel screen by the electrode material of preparation, in the pressure system 1 ~ 10 minute of 5 ~ 25MPa, obtained electrode is for subsequent use;
(3) taking calomel electrode as reference electrode, is to electrode with platinum electrode, and the electrode obtained with step (2), for work electrode, with the NaOH aqueous solution of pH=13.5 for electrolyte, prepares battery.
Battery is in-0.6 ~ 0V work, and with the rate charge-discharge of 4C, result as shown in Figs. 13 and 14.As can be seen from Figure 13, first all specific discharge capacities are 31.1 MAhs/g, and charge specific capacity is 31.7 MAhs/g, as can be seen from Figure 14, battery after circulation 500 weeks capability retention 98%.
embodiment 9
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.44mn 0.61ti 0.39o 2, concrete steps are:
(1) sodium acetate (CH is taken by the amount of substance ratio of Na:Mn:Ti=0.44:0.61:0.39 3cOONa), Mn nitrate (Mn (NO 3) 2) and butyl titanate (C 16h 36o 4ti), be dissolved in absolute ethyl alcohol respectively, under agitation the ethanol solution of sodium acetate and Mn nitrate is joined in the ethanol solution of carbonic acid four butyl ester gradually, and to add with the mol ratio of Na be that the citric acid of 10% is as complexing agent, heat 8 hours at 50 DEG C, form aqueous precursor gel gradually;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 2 hours at 600 DEG C in Muffle furnace, then 18 hours are processed at 750 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 0.61ti 0.39o 2.
What obtained by the present embodiment makes aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 6, positive electrode is similarly compound prepared by the present embodiment, difference is, the five nickel lanthanums of 2 quality % are adopted (to it should be noted that, here five nickel lanthanums have difunctional effect, play electron conduction on the one hand, another is convenient can absorb the hydrogen and oxygen that aqueous solution battery produces in charge and discharge process) replace active carbon as conductive additive, electrolyte adopts the Na of the 2mol/L of pH=13.5 2sO 4solution, adopt graphite felt as collector, and carry out electro-chemical test, method of testing is with embodiment 6.Voltage range 0 ~ 1.5V, test result is in table 1.
embodiment 10
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.44mn 0.78ti 0.22o 2, concrete steps are:
(1) sodium acetate (CH is taken by the amount of substance ratio of Na:Mn:Ti=0.44:0.78:0.22 3cOONa), Mn nitrate (Mn (NO 3) 2) and butyl titanate (C 16h 36o 4ti), be dissolved in absolute ethyl alcohol respectively, under agitation the ethanol solution of sodium acetate and Mn nitrate is joined in the ethanol solution of carbonic acid four butyl ester gradually, and to add with the mol ratio of Na be that the citric acid of 10% is as complexing agent, heat 8 hours at 60 DEG C, form aqueous precursor gel gradually;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 6 hours at 250 DEG C in Muffle furnace, then 15 hours are processed at 800 DEG C, gained brownish black material is of the present invention containing manganese and oxygen compound Na 0.44mn 0.78ti 0.22o 2.
What obtained by the present embodiment makes aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 6, positive electrode be similarly prepared by the present embodiment containing manganese and oxygen compound, difference is, adopt the five nickel lanthanums of 2% to replace active carbon as conductive additive, electrolyte adopts the Na of the 2M of pH=14 2sO 4solution, adopt stainless (steel) wire as collector, and carry out electro-chemical test, method of testing is with embodiment 6.Test voltage scope is 0V ~ 1.45V, and test result is in table 1.
embodiment 11
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.44mn 0.83ti 0.17o 2, concrete steps are:
(1) sodium acetate (CH is taken by the amount of substance ratio of Na:Mn:Ti=0.44:0.83:0.17 3cOONa), Mn nitrate (Mn (NO 3) 2) and butyl titanate (C 16h 36o 4ti), be dissolved in absolute ethyl alcohol respectively, under agitation the ethanol solution of sodium acetate and Mn nitrate is joined in the ethanol solution of carbonic acid four butyl ester gradually, and to add with the mol ratio of Na be that the citric acid of 10% is as complexing agent, heat 8 hours at 60 DEG C, form aqueous precursor gel gradually;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 4 hours at 400 DEG C in Muffle furnace, then 18 hours are processed at 850 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 0.83ti 0.17o 2.
What obtained by the present embodiment makes aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 6, positive electrode be the present embodiment prepare containing manganese and oxygen compound, difference is, the five nickel lanthanums adopting 2% are conductive additive, and electrolyte adopts the Na of the 2M of pH=12 2sO 4with the NaNO of 1mol 3solution, collector adopts graphite cake, and carries out electro-chemical test, and method of testing is with embodiment 6.Test voltage scope is 0V ~ 1.55V, and test result is in table 1.
embodiment 12
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.44mn 0.44ti 0.56o 2, concrete steps are:
(1) sodium acetate (CH is taken by the amount of substance ratio of Na:Mn:Ti=0.44:0.44:0.56 3cOONa), Mn nitrate (Mn (NO 3) 2) and butyl titanate (C 16h 36o 4ti), be dissolved in absolute ethyl alcohol respectively, mix and add with the mol ratio of Na be the citric acid of 10% as complexing agent, at 60 DEG C heat 8 hours, form aqueous precursor gel gradually;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 5 hours at 500 DEG C in Muffle furnace, then 18 hours are processed at 850 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.44mn 0.44ti 0.56o 2.
What obtained by the present embodiment makes aqueous solution sodium ion secondary battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 6, positive electrode be the present embodiment prepare containing manganese and oxygen compound, difference is, adopt the five nickel lanthanums of 2% to replace active carbon as conductive additive, electrolyte adopts the Na of the 1M of pH=11 2sO 4with the mixed solution of NaOH, adopt graphite felt as collector, and carry out electro-chemical test, method of testing is with embodiment 6.Test voltage scope is 0V ~ 1.6V, and test result is in table 1.
embodiment 13
The present embodiment is for illustration of the contrast using active carbon as the negative electrode active material of aqueous solution sodium ion secondary battery and material of the present invention.
The density of the active carbon that market is sold is generally 0.45-0.55g/cm 3, active carbon is prepared into sodium-ion battery, and concrete steps are with reference to embodiment 1.Use constant current charge-discharge pattern to test, discharging by voltage is 1.8V, and charging by voltage is 2.8V, carries out under test is respectively 1C current density.Test result is shown in Figure 15, and cyclical stability is shown in Figure 16.Found out by Figure 15, its 1C charge/discharge capacity is 25 MAhs/g, lower than material capacity of the present invention, and first all efficiency only has 85%.Material circulation good stability of the present invention as seen from Figure 16.Specifically, under electrode material 1C of the present invention, specific capacity is 35 MAhs/g, and circulate 200 weeks capability retentions 99%, first all efficiency 92%, and specific capacity 26 MAhs/g under active carbon 1C, first all efficiency 85%.Circulate 100 weeks capability retentions 97%.
embodiment 14
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.55mn 0.55ti 0.45o 1.99, concrete steps are:
(1) TiO is taken by the amount of substance ratio of Na:Mn:Ti=0.55:0.55:0.45 2, Mn 2o 3and Na 2cO 3, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, at Ar or N 2process 20h in atmosphere, at 950 DEG C, gained atrament is compound of the present invention containing manganese oxygen Na 0.55mn 0.55ti 0.45o 1.99.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and difference is pointed out to be, adopts Graphene to replace active carbon as conductive additive.Carry out electro-chemical test, method of testing is with embodiment 7.Test voltage scope is-0.62 ~ 0V, the results are shown in Table 2.
embodiment 15
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.50mn 0.48fe 0.02ti 0.50o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Fe:Ti=0.50:0.48:0.02:0.50 2cO 3, Mn 2o 3, Fe 2o 3and TiO 2, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 24h at 900 DEG C, gained brownish black material is of the present invention containing manganese and oxygen compound Na 0.50mn 0.48fe 0.02ti 0.50o 2.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and difference is, adopts carbon black to replace active carbon as conductive additive.Carry out electro-chemical test, method of testing is with embodiment 7.Test voltage scope is-0.65 ~ 0.04V, the results are shown in Table 2.
embodiment 16
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.40mn 0.37cr 0.03ti 0.60o 2.01, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Cr:Ti=0.40:0.37:0.03:0.60 2cO 3, Mn 2o 3, Cr 2o 3and TiO 2, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 20h at 1000 DEG C, gained green matter is of the present invention containing manganese and oxygen compound Na 0.40mn 0.37cr 0.03ti 0.60o 2.01.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and difference is, adopts phosphoric lanthanum to replace active carbon as conductive additive.Carry out electro-chemical test, method of testing is with embodiment 7.Test voltage scope is-0.61 ~ 0.05V, the results are shown in Table 2.
embodiment 17
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.35mn 0.35ti 0.65o 2concrete steps are:
(1) sodium acetate (CH is taken by the amount of substance ratio of Na:Mn:Ti=0.35:0.35:0.65 3cOONa), Mn nitrate (Mn (NO 3) 2) and butyl titanate (C 16h 36o 4ti), in whipping process, the ethanol solution of sodium acetate and Mn nitrate is joined in the ethanol solution of carbonic acid four butyl ester gradually, add with the mol ratio of Na be the citric acid of 10% as complexing agent, at 70 DEG C heat 7 hours, form aqueous precursor gel gradually;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 6 hours at 300 DEG C in Muffle furnace, then 16 hours are processed at 950 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.35mn 0.35ti 0.65o 2.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and carries out electro-chemical test, and method of testing is with embodiment 7.Test voltage scope is-0.6 ~ 0.02V, the results are shown in Table 2.
embodiment 18
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.3mn 0.9v 0.1o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:V=0.3:0.9:0.1 2cO 3, Mn 2o 3and V 2o 3, mixing, mixed grinding half an hour in agate mortar, obtains the precursor powder of black;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 12h at 850 DEG C, gained green matter is compound N a of the present invention 0.3mn 0.9v 0.1o 2.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and carries out electro-chemical test, and method of testing is with embodiment 7.Test voltage scope is-0.61 ~ 0.05V, the results are shown in Table 2.
embodiment 19
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.42mn 0.92cr 0.08o 2.01, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Cr=0.42:0.92:0.08 2cO 3, Mn 2o 3and Cr 2o 3, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 12h at 850 DEG C, gained atrament is of the present invention containing manganese and oxygen compound Na 0.42mn 0.92cr 0.08o 2.01.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and carries out electro-chemical test, and method of testing is with embodiment 7.Test voltage scope is-0.6 ~ 0V, the results are shown in Table 2.
embodiment 20
The present embodiment adopts sol-gel process preparation containing manganese and oxygen compound Na 0.44mn 0.95fe 0.05o 2, concrete steps are:
(1) sodium acetate ((CH is taken by the ratio of the amount of substance of Na:Mn:Fe=0.44:0.95:0.05 3cOONa), Mn nitrate (Mn (NO 3) 2) and ferrous oxalate, be dissolved in absolute ethyl alcohol respectively, add after mixing with the mol ratio of sodium be the citric acid of 8% as complexing agent, heat 5 hours at 80 DEG C, form aqueous precursor gel gradually;
(2) aqueous precursor gel that step (1) obtains is transferred to Al 2o 3in crucible, and preliminary treatment 6 hours at 300 DEG C in Muffle furnace, then 16 hours are processed at 950 DEG C, gained atrament is compound N a of the present invention 0.44mn 0.95fe 0.05o 2.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and carries out electro-chemical test, and method of testing is with embodiment 7.Test voltage scope is-0.6 ~ 0.05V, the results are shown in following table 2.
embodiment 21
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.55mn 0.40co 0.15ti 0.45o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Co:Ti=0.55:0.40:0.15:0.45 2cO 3, Mn 2o 3, Co 2o 3and TiO 2, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 20h at 1000 DEG C, gained green matter is compound N a of the present invention 0.55mn 0.40co 0.15ti 0.45o 2.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and carries out electro-chemical test, and method of testing is with embodiment 7.Test voltage scope is-0.61 ~ 0.05V, the results are shown in Table 2.
embodiment 22
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.38mn 0.35fe 0.03ti 0.62o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Fe:Ti=0.38:0.35:0.03:0.62 2cO 3, Mn 2o 3, Fe 2o 3and TiO 2, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 16h at 900 DEG C, gained reddish-brown material is of the present invention containing manganese and oxygen compound Na 0.38mn 0.35fe 0.03ti 0.62o 2.
What obtained by the present embodiment makes aqueous solution sodium-ion battery containing after manganese and oxygen compound grinding according to the preparation method of embodiment 7, and carries out electro-chemical test, and method of testing is with embodiment 7.Test voltage scope is-0.59 ~ 0.1V, the results are shown in Table 2.
embodiment 23
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.42mn 0.32v 0.10ti 058o 2, concrete steps are:
(1) Na is taken by the ratio of the amount of substance of Na:Mn:V:Ti=0.42:0.32:0.10:0.58 2cO 3, Mn 2o 3, V 2o 3and TiO 2, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, under Ar gas shielded atmosphere, in Muffle furnace, process 15h at 800 DEG C, gained atrament is compound N a of the present invention 0.42mn 0.32v 0.10ti 058o 2.
Make aqueous solution sodium-ion battery according to the preparation method of embodiment 7 after the compound grinding obtained by the present embodiment, and carry out electro-chemical test, method of testing is with embodiment 7.Test voltage scope is-0.6 ~ 0V, the results are shown in Table 2.
embodiment 24
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.43mn 0.3b 0.12ti 058o 2, concrete steps are:
(1) Na is taken by the ratio of the amount of substance of Na:Mn:B:Ti=0.44:0.32:0.12:0.58 2cO 3, Mn 2o 3, B 2o 3and TiO 2, mixing, mixed grinding half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, under Ar gas shielded atmosphere, in Muffle furnace, process 15h at 750 DEG C, gained atrament is compound N a of the present invention 0.43mn 0.3b 0.12ti 058o 2.
Make aqueous solution sodium-ion battery according to the preparation method of embodiment 7 after the compound grinding obtained by the present embodiment, and carry out electro-chemical test, method of testing is with embodiment 7.Test voltage scope is-0.6 ~ 0V, the results are shown in Table 2.
embodiment 25
The present embodiment adopts solid phase method preparation containing manganese and oxygen compound Na 0.4mn 0.5ti 0.5o 2, concrete steps are:
(1) Na is taken by the amount of substance ratio of Na:Mn:Ti=0.4:0.5:0.5 2cO 3, Mn 2o 3and TiO 2, mixing, ground and mixed half an hour in agate mortar, obtains precursor powder;
(2) precursor powder that step (1) obtains is transferred to Al 2o 3in crucible, in Muffle furnace, process 15h at 800 DEG C, gained atrament is compound N a of the present invention 0.4mn 0.5ti 0.5o 2.
Obtained for the present embodiment is contained manganese and oxygen compound coated with conductive polymer P Py, and concrete operation method is as follows:
A () is by pyrrole monomer and Na 0.4mn 0.5ti 0.5o 2powder fully disperses in acid diethyl ether solution, obtains mixed liquor A;
B () adds hydrogen peroxide and reacts in mixed liquor A, then gained reactant mixture is remained on ultrasonic 1 ~ 4h in 0 ~ 30 DEG C of water-bath, room temperature (about 25 DEG C) leaves standstill 1 ~ 2h again, after filtration, washing, drying, obtains the Na that conducting polymer PPy is coated 0.4mn 0.5ti 0.5o 2negative active core-shell material.
Above-mentioned negative active core-shell material is made water sodium-ion battery according to the preparation method of embodiment 7, and carries out electro-chemical test, method of testing is with embodiment 7.Test voltage scope is-0.6 ~ 0V, the results are shown in Table 2.
The sodium-ion battery electrochemical property test result of the full battery of table 1 embodiment 9 to 12 aqueous solution
Table 2 embodiment 14 to 25 aqueous solution sodium ion half-cell electrochemical property test result
Although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Be appreciated that and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.

Claims (9)

1. what be used as aqueous solution sodium ion secondary battery negative electrode active material contains a manganese and oxygen compound, it is characterized in that, the described general formula containing manganese and oxygen compound is: Na x[Mn (1-y)a y] O 2-z, wherein, 0.2≤x≤0.7,0≤y≤1.15-x and-0.02≤z≤0.02; Wherein, A is selected from one or more in B, Ti, Fe, V, Co, Al and Cr element.
2. according to claim 1 containing manganese and oxygen compound, it is characterized in that, in described general formula, 0.3≤x≤0.55,0≤y≤1.15-x and-0.01≤z≤0.01;
Preferably, 0.3≤x≤0.5,0≤y≤1.1-x and-0.01≤z≤0.01;
More preferably, x=0.44,0≤y≤1-x and-0.01≤z≤0.01.
3. prepare the method containing manganese and oxygen compound described in claim 1 or 2, it is characterized in that, described method is solid phase method or sol-gel process;
Described solid phase method comprises the following steps:
(1) by Na:Mn:A=(1.00 ~ 1.05) x:(1-y): the amount of substance of y, than the oxide of weighing sodium carbonate, manganese sesquioxide managnic oxide and A, obtains precursor powder after ground and mixed;
(2) precursor powder step (1) obtained, at 650 ~ 1000 DEG C, preferably, processes 8 ~ 25 hours at 800 ~ 1000 DEG C, such as, 12 ~ 24 hours, obtains described containing manganese and oxygen compound; And
Described sol-gel process comprises the following steps:
(1 ') is by Na:Mn:A=x:(1-y): the amount of substance of y is than taking sodium acetate, Mn nitrate and the salt containing A, be dissolved in absolute ethyl alcohol respectively, add complexing agent such as citric acid after mixing, heat 5 ~ 8 hours at 50 ~ 80 DEG C, obtain aqueous precursor gel;
The aqueous precursor gel that step (1 ') obtains by (2 ') preliminary treatment 2 ~ 6 hours at 250 ~ 600 DEG C, then 8 ~ 20 hours are processed at 750 ~ 1000 DEG C, obtain described containing manganese and oxygen compound.
4., for a negative pole for aqueous solution sodium ion secondary battery, it is characterized in that, described negative pole comprise conductive additive, binding agent, collector and as negative electrode active material claim 1 or 2 described in containing manganese and oxygen compound.
5. negative pole according to claim 4, is characterized in that, described conductive additive be selected from active carbon, five nickel lanthanums, carbon black, acetylene black, graphite powder, carbon nano-tube and Graphene one or more;
Preferably, described binding agent is polytetrafluoroethylene or Kynoar;
Preferably, described collector is nickel screen, titanium net, stainless (steel) wire, graphite felt or graphite cake.
6. an aqueous solution sodium ion secondary battery, is characterized in that, described aqueous solution sodium ion secondary battery comprises the negative pole described in claim 4 or 5.
7. aqueous solution sodium ion secondary battery according to claim 6, is characterized in that, the alkaline electrolyte that described aqueous solution sodium ion secondary battery also comprises positive pole and is placed between described positive pole and described negative pole.
8. described in claim 1 or 2 containing manganese and oxygen compound as the purposes of aqueous solution sodium ion secondary battery negative electrode active material.
9. the purposes of the aqueous solution sodium ion secondary battery described in claim 6 or 7 in the energy storage device of solar energy or wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
CN201410280131.XA 2014-06-20 2014-06-20 Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof Pending CN105185978A (en)

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