CN109830671A

CN109830671A - A kind of tunnel recombination structure material and the sodium-ion battery positive material using tunnel recombination structure material preparation

Info

Publication number: CN109830671A
Application number: CN201910169104.8A
Authority: CN
Inventors: 吴振国; 殷文泽; 郭孝东; 向伟; 钟本和
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2019-03-06
Filing date: 2019-03-06
Publication date: 2019-05-31

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 Na_0.44MnO₂The excellent cycle performance of material.

Description

It a kind of tunnel recombination structure material and is prepared using the tunnel recombination structure material Sodium-ion battery positive material

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 Na_0.44MnO₂(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, Na_0.44MnO₂Circulation 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 Na_0.44MnO₂Application 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 Cao_0.44MnO₂, 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 Na_0.44MnO₂, 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 Na_0.44MnO₂Influence (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 Na_0.44MnO₂Or 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 step_0.44MnO₂-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 Na_0.44MnO₂The 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 prepared_0.44MnO₂The 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 prepared_0.7MnO₂The electron microscope of layer structure；

Fig. 2 (b) is the Na that comparative example is prepared_0.44MnO₂The 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 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；

Fig. 1 (a) is the Na that the embodiment of the present invention 1 is prepared_0.44MnO₂The 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

1. a tunnel composite structure material, is characterized in that, is prepared according to the following method:

Step 1: Weigh the sodium salt, potassium salt, manganese salt and precipitant according to the metering ratio; wherein, the ratio of sodium, potassium and manganese metal ions is 0.5-0.6:0.1-0.2:1;

Step 2: First, dissolving sodium salt, potassium salt and manganese salt in deionized water to obtain solution A;

Step 3: Dissolve the precipitant in an appropriate amount of deionized water to obtain solution B;

Step 4: At room temperature, add solution B dropwise to solution A while stirring, and continue to stir for 0.5 to 4 h after the dropwise addition: after stirring, the remaining solvent is stirred and evaporated to dryness at 70-90 °C, and then the obtained precursor is Place in an oven at 120-180℃ for 10h;

Step 5: Finally, the dried precursor is calcined:

Step 6: Quenching the calcined sample with liquid nitrogen to finally obtain the layered tunnel composite structure material.

2 . The tunnel composite structure material according to claim 1 , wherein the precipitating agent is: oxalic acid, ammonium carbonate or ammonia water. 3 .

3 . The tunnel composite structure material according to claim 1 , wherein the specific measures for calcining in the step 5 are: first calcining at 300-450° C. for 4-8 hours, and then calcining at 700-1000° C. for 10 hours. 4 . -18h, the heating rate is 2-10°C/min.

4. A positive electrode material for a sodium ion battery, characterized in that, the positive electrode material is prepared from the tunnel composite structure material described in any one of claims 1-3 as a raw material.