CN104118913B - For the hydrothermal synthesis method of the iron sodium manganate of water system positively charged ion battery electrode material and the preparation method of water system battery - Google Patents

For the hydrothermal synthesis method of the iron sodium manganate of water system positively charged ion battery electrode material and the preparation method of water system battery Download PDF

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CN104118913B
CN104118913B CN201410384112.1A CN201410384112A CN104118913B CN 104118913 B CN104118913 B CN 104118913B CN 201410384112 A CN201410384112 A CN 201410384112A CN 104118913 B CN104118913 B CN 104118913B
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water system
sodium
source compound
iron
positively charged
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CN104118913A (en
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曹殿学
张莹
杜孟孟
程魁
叶克
王贵领
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Harbin Engineering University
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    • Y02E60/10—Energy storage using batteries

Abstract

The present invention is to provide a kind of hydrothermal synthesis method of the iron sodium manganate for water system positively charged ion battery electrode material and the preparation method of water system battery.(1) solution Fe source compound, manganese source compound being made into 0.5mol/L mixes mutually, adds bicarbonate of ammonia and dispersion agent made by ethanol, violent stirring 1h simultaneously; (2) mixing solutions that step (1) obtains is transferred to hydro-thermal reaction in reactor, by the throw out that obtains through suction filtration, cleaning, drying; (3) dried product is carried out ball milling with the sodium source compound of stoichiometric ratio and mix 3 ~ 10h; (4) mixture after ball milling is put into retort furnace and carry out pre-treatment and high-temperature calcination obtains final product Na 0.3fe 0.5mn 0.5o 2, be abbreviated as NFMO.Through electro-chemical test, material of the present invention under 10mA/g current density, 1mol/L? Na 2sO 4340mAh/g is can reach, 1mol/L in electrolytic solution? MgCl 2250mAh/g is can reach in electrolytic solution.Raw material sources is extensive, and easily, aqueous electrolyte cost is low, environment-protecting asepsis in preparation.

Description

For the hydrothermal synthesis method of the iron sodium manganate of water system positively charged ion battery electrode material and the preparation method of water system battery
Technical field
That the present invention relates to is a kind of preparation method for water system positively charged ion battery electrode material, specifically a kind of new electrode materials iron sodium manganate Na adopting Gong the multivalent state positively charged ion deintercalation of aqueous electrolyte 0.3fe 0.5mn 0.5o 2hydrothermal synthesis method.
Background technology
The world today is faced with day by day serious energy dilemma and environmental problem, and the green clean energy therefore developing reusable edible has become the important topic of the world today.Lithium ion battery due to its high-energy-density in the field of portable type electronic product successfully realize commercially produce, but earth lithium source resource-constrained, the heavy demand of industrialization lithium cell to metallic lithium causes the price increase of metallic lithium.Cost has become the key factor of lithium ion battery development gradually.Sodium is as laying in one of abundant element in the earth's crust, similar to lithium character, can well transmit electric charge, is expected to replace lithium and obtains development in large-scale energy storage device.
Up to now, people are to transition metal oxide Na xmO 2conduct extensive research.Delmas is by Na xmO 2mainly be divided into three groups: O3, P2 and P3, these structures are that what to occupy with sodium ion is that octahedral position (Octahedral) or triangular prism position (Prismatic) distinguish.Here M represents V, Cr, Fe, Mn, Co and Ni, and wherein, Fe and Mn element is due to minimum to environmental injury and cheap and enjoy favor.α-NaFeO 2with α-NaMnO 2all show electrochemical activity, but they only allow 0.4 Na (α-NaFeO respectively 2) and be less than 0.8 Na (α-NaMnO 2) reversible deintercalation.There are some researches show: in process of charging, α-NaFeO 2the Fe of high-spin can be generated 4+make structural instability.Although the Na of P2 phase 0.6mnO 2initial specific capacities be 160mAh/g, but the Na of P2 structure xfeO 2do not exist.Recently, Yabuuchi successfully prepares P2-Na 2/3fe 1/2mn 1/2o 2, initial specific capacities can reach 190mAh/g, after 30 chargings, still can keep 150mAh/g.As can be seen here, the Na of P2 phase 0.3fe 0.5mn 0.5o 2(NFMO) Na can be realized +reversible deintercalation is a kind of very promising novel anode material that can be used for secondary sodium-ion battery.But the solute that this material is used for current sodium-ion battery organic system electrolytic solution conventional is NaClO 4, NaTFSI and NaPF 6, conventional organic solvent has PC, EC, DMC, DME, DEC, THF, three methanol and dimethyl ethers and the mixture between them.Organic system electrolytic solution exists that cost is high, poor stability, poisonous shortcoming.But selection aqueous electrolyte, while the specific storage that maintenance is considerable, really can realize the world today to battery low cost, high security and environment amenable requirement.Therefore probe into the electrochemical behavior of NFMO material in aqueous electrolyte and seem particularly important.Specifically can see document J.Zhao, J.Xu, D.HoeLee, etal.ElectrochemicalandthermalpropertiesofP2-typeNa 2/3fe 1/2mn 1/2o 2forNa-ionbatteries.J.PowerSource, 264 (2014), 235. and J.Zhao, L.Zhao, N.Dimov, S.Okada, T.Nishida, J.Electrochem.Soc., 60 (2013), A3077.
Summary of the invention
The object of the present invention is to provide a kind of raw material sources extensive, easily, cost is low, the hydrothermal synthesis method of the iron sodium manganate for water system positively charged ion battery electrode material of environment-protecting asepsis in preparation.The present invention also aims to the preparation method that a kind of water system battery by being raw material with iron sodium manganate is provided.
The object of the present invention is achieved like this:
(1) solution Fe source compound, manganese source compound being made into 0.5mol/L mixes mutually, adds bicarbonate of ammonia and dispersion agent made by ethanol, violent stirring 1h simultaneously;
(2) mixing solutions that step (1) obtains is transferred to hydro-thermal reaction in reactor, by the throw out that obtains through suction filtration, cleaning, drying;
(3) dried product is carried out ball milling with the sodium source compound of stoichiometric ratio and mix 3 ~ 10h;
(4) mixture after ball milling is put into retort furnace and carry out pre-treatment and high-temperature calcination obtains final product Na 0.3fe 0.5mn 0.5o 2, be abbreviated as NFMO.
Described Fe source compound is ferrous sulfate, iron trichloride or iron nitrate.
Described manganese source compound is manganous sulfate, manganous nitrate or manganous chloride.
Described sodium source compound is sodium hydroxide, sodium carbonate or sodium bicarbonate.
The present invention with the preparation method of the water system battery that iron sodium manganate is raw material is: electrode pastes by binding agent polyvinylidene difluoride (PVDF) PVDF, acetylene black AB, NNMO in mass ratio 10%:10%:80% be mixed, dry at 80 DEG C on carbon cloth electrode pastes being coated in 1cm × 1cm, be to electrode with carbon-point, saturated calomel electrode is reference electrode, 1mol/LNa 2sO 4, MgCl 2the aqueous solution is electrolytic solution, is assembled into the water system battery of three-electrode system together.
Invention is by element ferrimanganic mol ratio 1:1 with Fe source compound, manganese source compound, add the bicarbonate of ammonia being four times in iron, manganese amount of substance sum simultaneously, add ethanol simultaneously and make dispersion agent, ferrimanganic carbonate precursor is obtained by hydrothermal method, then dried presoma is mixed with sodium source compound ball milling, after drying, carry out pre-treatment in air atmosphere, calcining finally obtains product Na 0.3fe 0.5mn 0.5o 2(being abbreviated as NFMO).Can reversible deintercalation Na by synthesis +, Mg 2+new electrode materials NFMO, make full use of earth affluent resources sodium salt, magnesium salts, adopt 1mol/LNa 2sO 4, MgCl 2the aqueous solution, as electrolytic solution, develops a kind of secondary water system battery of low cost.
Advantage of the present invention is:
(1) spherical carbonic acid ferrimanganic presoma has first been synthesized by hydrothermal method, then by high-temperature calcination process, react with sodium source and generate transition metal oxide NFMO, nano level primary granule constitutes micron-sized secondary granule, this is conducive to electrode materials NFMO and electrolytic solution bump contact, be convenient to the quick exchange of ion between solid phase and liquid phase, the evolving path shortened between solid phase particles is conducive to Na +solid-phase media inside is entered fast from surface;
(2) the flammable explosive organic electrolyte of abandoning tradition, effectively utilize the sodium sulfate of safety non-toxic cheapness, magnesium chloride brine, to zero environmental, discharge zero burden, really realize environmental protection, and specific heat of water holds, and there will not be the phenomenon that battery is overheated large, can prevent the battery explosion phenomenon that maloperation (such as over-charging of battery) causes, safety coefficient is high;
(3) ionic conductivity of aqueous electrolyte is higher than organic electrolyte, because electrolytic solution impedance is little, has less potential drop, can carry out high rate charge-discharge;
(4) raw material all adopts the affluent resources that the earth has, and such as inorganic sodium, magnesium salts, simple and easy to get, with low cost.
Through electro-chemical test, material of the present invention under 10mA/g current density, 1mol/LNa 2sO 4340mAh/g is can reach, 1mol/LMgCl in electrolytic solution 2250mAh/g is can reach in electrolytic solution.Raw material sources is extensive, and easily, aqueous electrolyte cost is low, environment-protecting asepsis in preparation.
Accompanying drawing explanation
Fig. 1 is the Na under embodiment 1 synthesis condition 0.3fe 0.5mn 0.5o 2(NFMO) XRD figure.
Fig. 2 (a)-Fig. 2 (c) is Na 0.3fe 0.5mn 0.5o 2(NFMO) at 1mol/LNa 2sO 4chemical property figure (embodiment 5) in electrolytic solution: Fig. 2 (a) constant current charge-discharge graphic representation; Fig. 2 (b) cyclic voltammogram; Fig. 2 (c) EIS impedance spectrogram.
Fig. 3 (a)-Fig. 3 (c) is Na 0.3fe 0.5mn 0.5o 2(NFMO) at 1mol/LMgCl 2chemical property figure (embodiment 7) in electrolytic solution: Fig. 3 (a) constant current charge-discharge graphic representation; Fig. 3 (b) cyclic voltammogram; Fig. 3 (c) EIS impedance spectrogram.
Embodiment
In order to effect of the present invention is described better, be illustrated with specific examples below.
Embodiment 1
(1) by FeSO 4, MnSO 4be made into 0.5mol/L solution according to ferrimanganic stoichiometric ratio and mutually drip mixing, add NH simultaneously 4hCO 3and dispersion agent made by ethanol, violent stirring 1h;
(2) above mixing solutions is transferred to hydro-thermal reaction in teflon-lined stainless steel cauldron, hydrothermal condition is 180 DEG C, 12h, by the throw out that obtains through suction filtration, cleaning, drying; ;
(3) by after dried product with the Na of stoichiometric ratio 2cO 3carry out ball milling mixing 5h;
(4) mixture after ball milling is put into that retort furnace carries out 400 DEG C, 6h pre-treatment and 880 DEG C, 24h high-temperature calcination obtain final product NFMO.
Can find out from XRD figure: feature peak-to-peak type is sharp-pointed, without obvious impurity peaks, shows that product degree of crystallinity is intact, purity is high.Embodiment 1 is optimum synthesis condition.
Embodiment 2
Change embodiment 1 (2) hydrothermal condition into 150 DEG C, 12h.All the other synthesis conditions are constant.
Embodiment 3
Embodiment 1 (4) is changed into the mixture after by ball milling and put into that retort furnace carries out 400 DEG C, 6h pre-treatment and 800 DEG C, 24h high-temperature calcination obtain final product NFMO.All the other synthesis conditions are constant.
Embodiment 4
Embodiment 1 (4) is changed into the mixture after by ball milling and put into that retort furnace carries out 400 DEG C, 6h pre-treatment and 700 DEG C, 24h high-temperature calcination obtain final product NFMO.All the other synthesis conditions are constant.
Embodiment 5
By the NFMO electrode slice under embodiment 1 synthesis condition and binding agent polyvinylidene difluoride (PVDF) PVDF, acetylene black AB in mass ratio 80%:10%:10% be mixed and made into electrode pastes, dry at 80 DEG C on the carbon cloth being coated in 1cm × 1cm, be the water system battery of reference electrode composition three-electrode system to electrode, saturated calomel electrode with carbon-point.By this battery at 1mol/LNa 2sO 4the test of EIS impedance analysis, cyclic voltammetry and constant current charge-discharge is carried out in the aqueous solution.
Embodiment 6
By the NFMO electrode slice under embodiment 1 synthesis condition and binding agent polyvinylidene difluoride (PVDF) PVDF, acetylene black AB in mass ratio 80%:10%:10% be mixed and made into electrode pastes, dry at 80 DEG C on the carbon cloth being coated in 1cm × 1cm, be the water system battery of reference electrode composition three-electrode system to electrode, saturated calomel electrode with carbon-point.By this battery at 0.5mol/LNa 2sO 4the test of EIS impedance analysis, cyclic voltammetry and constant current charge-discharge is carried out in the aqueous solution.
Embodiment 7
By the NFMO electrode slice under embodiment 1 synthesis condition and binding agent polyvinylidene difluoride (PVDF) PVDF, acetylene black AB in mass ratio 80%:10%:10% be mixed and made into electrode pastes, dry at 80 DEG C on the carbon cloth being coated in 1cm × 1cm, be the water system battery of reference electrode composition three-electrode system to electrode, saturated calomel electrode with carbon-point.By this battery at 1mol/LMgCl 2the test of EIS impedance analysis, cyclic voltammetry and constant current charge-discharge is carried out in the aqueous solution.
Embodiment 8
By the NFMO electrode slice under embodiment 1 synthesis condition and binding agent polyvinylidene difluoride (PVDF) PVDF, acetylene black AB in mass ratio 80%:10%:10% be mixed and made into electrode pastes, dry at 80 DEG C on the carbon cloth being coated in 1cm × 1cm, be the water system battery of reference electrode composition three-electrode system to electrode, saturated calomel electrode with carbon-point.By this battery at 0.5mol/LMgCl 2the test of EIS impedance analysis, cyclic voltammetry and constant current charge-discharge is carried out in the aqueous solution.

Claims (6)

1., for a hydrothermal synthesis method for the iron sodium manganate of water system positively charged ion battery electrode material, it is characterized in that:
(1) solution Fe source compound, manganese source compound being made into 0.5mol/L mixes mutually, adds bicarbonate of ammonia and dispersion agent made by ethanol, violent stirring 1h simultaneously;
(2) mixing solutions that step (1) obtains is transferred to hydro-thermal reaction in reactor, by the throw out that obtains through suction filtration, cleaning, drying;
(3) dried product is carried out ball milling with the sodium source compound of stoichiometric ratio and mix 3 ~ 10h;
(4) mixture after ball milling is put into retort furnace and carry out pre-treatment and high-temperature calcination obtains final product Na 0.3fe 0.5mn 0.5o 2, be abbreviated as NFMO.
2. the hydrothermal synthesis method of the iron sodium manganate for water system positively charged ion battery electrode material according to claim 1, is characterized in that: described Fe source compound is ferrous sulfate, iron trichloride or iron nitrate.
3. the hydrothermal synthesis method of the iron sodium manganate for water system positively charged ion battery electrode material according to claim 1 and 2, is characterized in that: described manganese source compound is manganous sulfate, manganous nitrate or manganous chloride.
4. the hydrothermal synthesis method of the iron sodium manganate for water system positively charged ion battery electrode material according to claim 1 and 2, is characterized in that: described sodium source compound is sodium hydroxide, sodium carbonate or sodium bicarbonate.
5. the hydrothermal synthesis method of the iron sodium manganate for water system positively charged ion battery electrode material according to claim 3, is characterized in that: described sodium source compound is sodium hydroxide, sodium carbonate or sodium bicarbonate.
6. the preparation method of the iron sodium manganate obtained with method described in the claim 1 water system battery that is raw material, it is characterized in that: electrode pastes by binding agent polyvinylidene difluoride (PVDF), acetylene black, NFMO in mass ratio 10%:10%:80% be mixed, dry at 80 DEG C on carbon cloth electrode pastes being coated in 1cm × 1cm, be to electrode with carbon-point, saturated calomel electrode is reference electrode, 1mol/LNa 2sO 4, MgCl 2the aqueous solution is electrolytic solution, and be assembled into the water system battery of three-electrode system together, described NFMO prepares just like below method:
(1) solution Fe source compound, manganese source compound being made into 0.5mol/L mixes mutually, adds bicarbonate of ammonia and dispersion agent made by ethanol, violent stirring 1h simultaneously;
(2) mixing solutions that step (1) obtains is transferred to hydro-thermal reaction in reactor, by the throw out that obtains through suction filtration, cleaning, drying;
(3) dried product is carried out ball milling with the sodium source compound of stoichiometric ratio and mix 3 ~ 10h;
(4) mixture after ball milling is put into retort furnace and carry out pre-treatment and high-temperature calcination.
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