CN109830671A - A kind of tunnel recombination structure material and the sodium-ion battery positive material using tunnel recombination structure material preparation - Google Patents
A kind of tunnel recombination structure material and the sodium-ion battery positive material using tunnel recombination structure material preparation Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 230000006798 recombination Effects 0.000 title claims abstract description 28
- 238000005215 recombination Methods 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000001103 potassium chloride Substances 0.000 claims abstract description 9
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 230000000171 quenching effect Effects 0.000 claims abstract description 4
- 239000013557 residual solvent Substances 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020510 Na4Mn9O18 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- LZFMACRHJXVTIV-UHFFFAOYSA-N [F].C(=C)Cl Chemical compound [F].C(=C)Cl LZFMACRHJXVTIV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of tunnel recombination structure material and the sodium-ion battery positive material using tunnel recombination structure material preparation, the material are prepared in accordance with the following methods: step 1: by metering than weighing sodium salt, sylvite, manganese salt and precipitating reagent；Step 2: sodium salt, sylvite and manganese salt being dissolved in deionized water and obtain solution A；Step 3: precipitating reagent being dissolved in appropriate amount of deionized water and obtains solution B；Rapid 4: under room temperature, solution B being added drop-wise in solution A while stirring, continues 0.5~4h of stirring after dripping: residual solvent being stirred at 70-90 DEG C after stirring and is evaporated, gained predecessor is then placed in 120-180 DEG C of baking oven dry 10h；Step 5: the predecessor after drying being calcined: step 6: by calcined sample using Quenching in liquid nitrogen, finally obtaining the tunnel recombination structure material of stratiform.The application composite material combines KMn8O16The high-energy density of material, high rate capability and Na0.44MnO2The excellent cycle performance of material.
Description
Technical field
It is answered the present invention relates to chemical technology field more particularly to a kind of tunnel recombination structure material and using the tunnel
Close the sodium-ion battery positive material of structural material preparation.
Background technique
With the consumption of fossil fuel and increasingly sharpening for environmental pollution, to renewable energy (wind energy, solar energy, tide
Can be equal) utilization more and more attention has been paid to the development of extensive energy storage technology is also increasingly taken seriously.Lithium ion battery at present
Have been obtained successful application in energy storage field, but the reserves of lithium resource are limited and be unevenly distributed, lithium ion battery at
The problems such as this is high limits lithium ion battery in the large-scale application of energy storage field.Due to the rich reserves of sodium and cheap and easy to get,
Along with sodium ion and lithium ion have similar electrochemistry, so that sodium-ion battery becomes lithium ion battery and leads in energy storage
A kind of feasible substitute technology in domain.But the research of the electrode material about sodium-ion battery is still in the primary stage.It grinds at present
Studying carefully more sodium-ion battery positive material has polyanionic material, stratified material, tunnel structure material and organic material.Its
Middle tunnel structure Mn-based material has preferable structural stability and open alkali metal ion diffusion admittance, as sodium-ion battery
Anode shows excellent cycle performance and high rate performance when using.KMn8O16And Na0.44MnO2(with Na4Mn9O18It is identical) it is two
Typical tunnel structure is planted, wherein KMn8O16Energy density with higher and high rate performance, but cyclical stability is poor,
Na0.44MnO2Circulation and high rate performance be dominant, but theoretical specific energy is lower, can by building " tunnel-tunnel " composite construction
To combine the advantage of two kinds of materials, the tunnel type manganese based composites haveing excellent performance are obtained.However, existing research focuses mostly in list
One tunnel structure, is concentrated mainly on Na0.44MnO2Application of the material in sodium electricity, to KMn8O16Tunnel type investigation of materials there has been no
Report, then less relate to the composite material of the two.
The good equal Na that nanometer threadiness is prepared for by Polymer-pyrolysis method more than Wuhan University Cao0.44MnO2, calcined by optimization
The temperature and improving chemical property of material (bibliography 1Cao, Y.；Xiao,L.；Wang,W.；Choi,D.；Nie,Z.；Yu,
J.；Saraf,L.V.；Yang,Z.；Liu,J.Reversible Sodium Ion Insertion in Single
Crystalline Manganese Oxide Nanowires with Long Cycle Life.Advanced Materials
2011,23(28),3155.).Northeastern University Dai Kehua etc. passes through polyvinylpyrrolidone (PVP) gel auxiliary combustion legal system
For rodlike Na0.44MnO2, and investigated influence of the calcination temperature to material electrochemical performance.(bibliography 2Dai, K.H.；
Mao,J.；Song,X.Y.；Battaglia,V.；Liu,G.Na0.44MnO2with very fast sodium diffusion
and stable cycling synthesized via polyvinylpyrrolidone-combustion method.J
Power Sources 2015,285,161.).In addition, the Ma Guangyao etc. of China Mining University has studied starting material
MnCO3To finished product Na0.44MnO2Influence (the bibliography 3Ma, G. of chemical property；Zhao,Y.；Huang,K.；Ju,Z.；
Liu,C.；Hou,Y.；Xing,Z.Effects of the starting materials of Na0.44MnO2cathode
materials on their electrochemical properties for Na-
ionbatteries.Electrochimica Acta 2016,222,36.).Hubei University Zheng Hao etc. passes through rheology phase
Method is prepared for rodlike KMn8O16Material, and have studied its application in lithium ion battery.(referring to document 4Zheng, H.；
Feng,C.；Kim,S.-J.；Yin,S.；Wu,H.；Wang,S.；Li,S.Synthesis and electrochemical
properties of KMn8O16nanorods for Lithium ion batteries.Electrochimica Acta
2013,88,225.).Australian University of Wollongong Zhao Chaofeng etc. has been synthesized by hydro-thermal method by KMn8O16Nanowire
The nanocluster constituted is tieed up, and synthetic technological condition is optimized (referring to document 5Zhang, C.；Feng,C.；Zhang,
P.；Guo,Z.；Chen,Z.；Li,S.；Liu,H.K0.25Mn2O4nanofiber microclusters as high power
cathode materials for rechargeable lithium batteries.RSC Adv.2012,2(4),1643.)
Above method is to single tunnel structure Na0.44MnO2Or KMn8O16Research, and lay particular emphasis on the preparation work of material
Skill optimization is limited to the inherent shortcoming of single structure although achieving relatively excellent chemical property, result still without
Method meets the growth requirement of sodium-ion battery.
Summary of the invention
It is an object of the invention to solve the problems of the above-mentioned prior art, forged by coprecipitation method combination solid phase
It burns, Na is prepared in a step0.44MnO2-KMn8O16" tunnel-tunnel " composite material constituted, in conjunction with the excellent of two kinds of tunneling materials
Point obtains excellent chemical property.
A kind of tunnel recombination structure material, is prepared in accordance with the following methods:
Step 1: by metering than weighing sodium salt, sylvite, manganese salt and precipitating reagent；Wherein, the ratio of sodium, potassium, manganese Metal ion
For 0.5~0.6:0.1~0.2:1；
Step 2: sodium salt, sylvite and manganese salt being dissolved in deionized water obtain solution A first；
Step 3: precipitating reagent being dissolved in appropriate amount of deionized water and obtains solution B；
Step 4: under room temperature, solution B is added drop-wise in solution A while stirring, continue after dripping stirring 0.5~
4h: stirring at 70-90 DEG C by residual solvent after stirring and be evaporated, then gained predecessor is placed on to 120-180 DEG C of baking oven
Middle dry 10h；
Step 5: finally the predecessor after drying is calcined:
Step 6: calcined sample being used into Quenching in liquid nitrogen, finally obtains the tunnel recombination structure material of stratiform.
Further, tunnel recombination structure material as described above, the precipitating reagent are as follows: oxalic acid, ammonium carbonate or ammonium hydroxide.
Further, tunnel recombination structure material as described above, the concrete measure calcined in the step 5 are as follows: first
4-8h is calcined at 300-450 DEG C, 10-18h is then calcined at 700-1000 DEG C, and heating rate is 2-10 DEG C/min.
A kind of sodium-ion battery positive material, the positive electrode is with claim any tunnel recombination structure material as above
Material is prepared for raw material.
The utility model has the advantages that
It was noted that both for Mn base anode material, and main structure is tunnel structure, therefore, the present invention proposes logical
Material rate is overregulated, the composite material of two kinds of tunnel structures is prepared by one-step method, and utilize the collaboration of composite material
Effect obtains the electrode material haveing excellent performance.
The application uses Co deposited synthesis novel tunnel sandwich, which combines KMn8O16Material
High-energy density, high rate capability and Na0.44MnO2The excellent cycle performance of material.
Detailed description of the invention
Fig. 1 (a) is the Na that the embodiment of the present invention 1 is prepared0.44MnO2The electron microscope of tunnel structure；
Fig. 1 (b) is the KMn that the embodiment of the present invention 1 is prepared8O16The electron microscope of tunnel structure；
Fig. 2 (a) is the Na that comparative example is prepared0.7MnO2The electron microscope of layer structure；
Fig. 2 (b) is the Na that comparative example is prepared0.44MnO2The electron microscope of tunnel structure；
Fig. 3 is the cycle performance test chart of 2 tunnel recombination structure material of the embodiment of the present invention；
Fig. 4 is the high rate performance test chart of 2 tunnel recombination structure material of the embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1:
Tunnel recombination structure material preparation method of the present invention the following steps are included:
Step 1: by metering than weighing sodium salt, sylvite, manganese salt and precipitating reagent；Wherein, the ratio of sodium, potassium, manganese Metal ion
For 0.5~0.6:0.1~0.2:1；
Step 2: sodium salt, sylvite and manganese salt being dissolved in deionized water obtain solution A first；
Step 3: precipitating reagent being dissolved in appropriate amount of deionized water and obtains solution B；
Step 4: under room temperature, solution B is added drop-wise in solution A while stirring, continue after dripping stirring 0.5~
4h: stirring at 70-90 DEG C by residual solvent after stirring and be evaporated, then gained predecessor is placed on to 120-180 DEG C of baking oven
Middle dry 10h；
Step 5: finally the predecessor after drying is calcined under air atmosphere in Muffle furnace:, first at 300-450 DEG C
4-8h is calcined, 10-18h is then calcined at 700-1000 DEG C, heating rate is 2-10 DEG C/min；
Step 6: calcined sample being used into Quenching in liquid nitrogen, finally obtains the tunnel recombination structure material of stratiform.
Fig. 1 (a) is the Na that the embodiment of the present invention 1 is prepared0.44MnO2The electron microscope of tunnel structure；Fig. 1 (b) is this hair
The KMn that bright embodiment 1 is prepared8O16The electron microscope of tunnel structure；By Fig. 1 (a), Fig. 1 (b) as can be seen that passing through this hair
The material structure that bright embodiment is prepared is tunnel-tunnel recombination structure.
Comparative example:
The preparation method of the present embodiment the difference from embodiment 1 is that: in step 1 that sylvite is not added.
Fig. 2 (a), Fig. 2 (b) are stratiform-tunnel recombination structure material that this comparative example is prepared, and pass through Fig. 2 (a), Fig. 2
(b) as can be seen that the sandwich that this comparative example is prepared is stratiform-tunnel recombination structure, it can be seen that, the application
Related material structure is as shown in Figure 1 that two kinds of tunnel structures are compound, and the material that comparative example is prepared as shown in Fig. 2,
For stratiform-tunnel recombination structure, Cong Tuzhong is this it appears that the structure of the two is different.
Embodiment 2:
Tunnel-tunnel recombination structure Mn-based material that the embodiment of the present invention 1 is prepared is used for sodium-ion battery anode
Material has following steps:
Step 1: weigh in proportion it is a certain amount of gather inclined fluorine vinyl chloride (PVDF) binder and be put in weighing bottle, measure a certain amount of
N-Methyl pyrrolidone (NMP) be added weighing bottle, stirring.
Step 2: weighing layered tunnel recombination structure material and acetylene black in proportion, grinding uniformly, is added and weighs
Bottle stirs 10h, is uniformly mixed and obtains slurries；
Step 3: aluminium foil is pressed into the disk that diameter is 1.6cm, it is then coarse under 10MPa pressure, successively with 10%
Hydrochloric acid, deionized water, acetone cleaning, vacuum drying weigh weight, are denoted as weight 1, the slurries that step 2 mixes up uniformly are applied
It smears on the aluminium foil handled well, 80 DEG C of vacuum dry 12h, weighs weight, be denoted as weight 2.
Step 4: dry pole piece being moved on in glove box, using homemade sodium piece as anode, assembles 2025 button cells.
Electrolyte PC/EC (1:1v/v) solution that 1M NaClO4 is conductive salt.By the battery seal of assembling, static 10h makes to be electrolysed
Liquid is fully penetrated in the battery.
Step 5: by assembled battery, chemical property is tested in constant current on charge-discharge test instrument.Wherein charging or discharging current is close
Degree is set according to experimental design, and voltage range is in 1.5-4.3V.
Fig. 3 is the cycle performance test chart of tunnel recombination of embodiment of the present invention structure material；Fig. 4 is tunnel of the embodiment of the present invention
The high rate performance test chart of road sandwich can be seen that the tunnel being prepared using the method for the present invention by Fig. 3, Fig. 4
Road sandwich has excellent high rate capability and cycle performance.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (4)
1. a kind of tunnel recombination structure material, which is characterized in that be prepared in accordance with the following methods:
Step 1: by metering than weighing sodium salt, sylvite, manganese salt and precipitating reagent；Wherein, sodium, potassium, manganese Metal ion ratio be 0.5
~0.6:0.1~0.2:1；
Step 2: sodium salt, sylvite and manganese salt being dissolved in deionized water obtain solution A first；
Step 3: precipitating reagent being dissolved in appropriate amount of deionized water and obtains solution B；
Step 4: under room temperature, solution B being added drop-wise in solution A while stirring, continues 0.5~4h of stirring after dripping: stirring
Residual solvent is stirred at 70-90 DEG C after mixing and is evaporated, then gained predecessor is placed in 120-180 DEG C of baking oven dry
10h；
Step 5: finally the predecessor after drying is calcined:
Step 6: calcined sample being used into Quenching in liquid nitrogen, finally obtains the tunnel recombination structure material of stratiform.
2. tunnel recombination structure material according to claim 1, which is characterized in that the precipitating reagent are as follows: oxalic acid, ammonium carbonate
Or ammonium hydroxide.
3. tunnel recombination structure material according to claim 1, which is characterized in that calcines in the step 5 specifically arranges
It applies are as follows: 4-8h to be calcined at 300-450 DEG C first, then calcines 10-18h at 700-1000 DEG C, heating rate is 2-10 DEG C/
Minute.
4. a kind of sodium-ion battery positive material, which is characterized in that the positive electrode is multiple with any tunnel claim 1-3
Structural material is closed to be prepared for raw material.
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Cited By (1)
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| CN114180633A (en) * | 2020-09-15 | 2022-03-15 | 中国科学院大连化学物理研究所 | Preparation method and application of sodium manganate |
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