CN109712821A - A kind of CuMn2O4/MnxOyThe preparation of composite material and its test method of chemical property - Google Patents

Abstract

The invention belongs to technical field of composite preparation, disclose a kind of CuMn₂O₄/Mn_xO_yThe preparation of composite material and its test method of chemical property；By KOH and NaOH deionized water dissolving, wiring solution-forming A；By the Cu (CH of 0.5mol/L₃COO)₂Solution pours into the Mn (CH of 1.0mol/L₃COO)₂Wiring solution-forming B in solution；Solution B is added dropwise in solution A；Mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, reacts for 24 hours under the conditions of 180 DEG C, is centrifugated product after natural cooling；Substance after separation is placed in tube furnace and is dried, in air atmosphere 500 DEG C of calcining 5h, natural cooling.Material prepared by the present invention passes through electrochemical property test, it can be seen that after it have passed through multiple charge and discharge cycles, which has good high rate performance and cycle performance.

Description

A kind of CuMn2O4/MnxOyThe preparation of composite material and its test of chemical property Method

Technical field

The invention belongs to technical field of composite preparation more particularly to a kind of CuMn₂O₄/Mn_xO_yThe preparation of composite material And its test method of chemical property.

Background technique

Currently, the prior art commonly used in the trade is such that transition metal oxide due to its unique chemical property It is frequently used to the electrode active material as supercapacitor.Wherein Mn oxide (the Mn in transition metal oxide_xO_y) tool Have low cost, oxidation state variable, excellent cycle performance and higher capacitance and widely studied.The oxide of Mn There are many forms, such as: MnO₂, Mn₂O₃, Mn₃O₄Deng wherein MnO₂Application at most.It can be prepared using the method for co-precipitation MnO₂Nanoparticle can prepare Mn using hydro-thermal method₂O₃Nanoparticle, there are also some studies have shown that in Mn₂O₃It is adulterated in material The capacitance of composite material can be improved in carbon material.

It is few at present for the research of mangaic acid copper and preparation method thereof, be with stannous chloride and potassium permanganate in the prior art Raw material will undergo dissolution, nitrogen protection, stirring, ageing, washing, hydro-thermal, calcining during preparing mangaic acid copper.Entirely Process experiment step is many and diverse, and the time cycle is also longer.

In conclusion problem of the existing technology is:

(1) during preparing mangaic acid copper as raw material using stannous chloride and potassium permanganate in the prior art, due to introducing Chloride ion will pass through multiple water-washing step in the last handling process of material, and operating process is complicated, time-consuming, even so, It is difficult chloride ion of going out completely, in last high-temperature burning process, chloride ion is still remained in the product, leads to material not It is pure.

(2) O3 catalytic oxidation depollution technical aspect is mainly used for by the mangaic acid copper product of prior art preparation.This The mangaic acid copper of invention is mainly used for the electrode material of capacitor, and the process of capacitor charging/discharging is that ion is adsorbed in positive and negative anodes in fact With the process of migration, so material have big specific surface area will greatly improve specific capacitance.Meanwhile fake capacitance be metal from The capacitance having when redox reaction, Mn ion generation oxygen only therein in the mangaic acid copper product of one-component occur for son Change reduction reaction, so specific capacitance is not just high.

Solve the difficulty and meaning of above-mentioned technical problem: the raw material used in the prior art have born defect, produce Chloride ion in object is difficult to remove, meanwhile, existing technology is that mangaic acid copper is prepared by solvent-thermal method, is selected in this method Ethyl alcohol is as solvent.It is compared to hydro-thermal method, the cost of such method is higher.The present invention passes through hydro-thermal method and subsequent heat treatment phase In conjunction with method prepare CuMn₂O₄/Mn_xO_yComposite material.For the raw material used for acetate, acetate ion therein can be with It is completely removed in the follow-up heat treatment process by thermal decomposition.During the preparation process since two methods act synergistically to obtain A kind of composite material has fake capacitance, therefore, the composite wood wherein redox can occur for the manganese ion of two classes Expect specific capacity with higher, and preparation process is relatively easy, the time can be saved.

Summary of the invention

In view of the problems of the existing technology, the present invention provides a kind of CuMn₂O₄/Mn_xO_yComposite material, the composite wood Material is compared to single CuMn₂O₄Material, the composite material, there are more hole and defect, can be improved between lattice Insertion and abjection quantity and migration rate of the ion between lattice, improve the capacity and high rate performance of material.CuMn₂O₄/Mn_xO_y Electrode material of the composite material generally as supercapacitor.

The invention is realized in this way a kind of CuMn with outstanding high rate performance₂O₄/Mn_xO_yThe preparation side of composite material Method are as follows:

Step 1: by 3.00gKOH and 1.50gNaOH 20mL deionized water dissolving, wiring solution-forming A；

Step 2: by the Cu (CH of 5mL0.5mol/L₃COO)₂Solution pours into the Mn (CH of 5mL1.0mol/L₃COO)₂Solution Middle wiring solution-forming B；

Step 3: under agitation, solution B is added dropwise in solution A；

Step 4: after being added dropwise to complete, mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, 180 It reacts under the conditions of DEG C for 24 hours, is centrifugated product after cooled to room temperature；

Step 5: the substance after separation being placed in tube furnace and is dried, in air atmosphere 500 DEG C of calcining 5h, natural Cooling.

Further, the CuMn₂O₄/Mn_xO_yThe physical property of composite material carries out test characterization, XRD by XRD and SEM Test uses Empyrean x-ray diffractometer, and pipe presses 40kV, the Cu target K of Guan Liu 40mA, λ=0.15406nm_αRay；SEM Test uses acceleration voltage for the JSM-6360LV scanning electron microscope of 25kV.

Another object of the present invention is to provide CuMn₂O₄/Mn_xO_yThe electrochemical property test method of material, this method Are as follows:

Step 1: with the CuMn of preparation₂O₄/Mn_xO_yAs a positive electrode active material, acetylene black is as conductive agent, PTFE for material As binder, it is uniformly mixed according to the ratio of mass ratio 8:1:1, anode electrode piece is made；

Step 2: using capacitor active carbon as negative electrode active material, acetylene black as conductive agent, PTFE as binder, It is uniformly mixed also according to the ratio of mass ratio 8:1:1, negative electricity pole piece is made；

Step 3: to be saturated KNO₃Solution is assembled into water system button cell as electrolyte；

Step 4: using the prepared button cell of LANHE battery test system measurement, electrochemical workstation measurement circulation The AC impedance of volt-ampere curve and material before and after charge and discharge.

In conclusion advantages of the present invention and good effect are as follows:

Mangaic acid copper product is prepared in the prior art using stannous chloride and potassium permanganate as raw material, first 180 DEG C of hydro-thermal 15h, so It to be also aged 12h afterwards, it is subsequent also to want 600 DEG C of calcining 2h.The whole preparation process time cycle is longer, and Cl^-More difficult removing.This Invention is raw material using copper acetate and manganese acetate, and reduces the time of ageing in preparation process, shortens preparation week Phase, while the removing of acetate ion is relatively simple, can remove in calcination process.

The present invention is regulated and controled using potassium hydroxide and sodium hydroxide as raw material using a water acetic acid copper and four water acetic acid manganese as raw material Alkaline environment is successively prepared for CuMn by hydrothermal synthesis and the method for high-temperature calcination₂O₄/Mn_xO_yComposite material, by material Material carries out maximum specific discharge capacity of electrochemical property test material under the conditions of 0.1CA/g and has reached 164.6F/g.? Under the current density of 0.2A/g after charge and discharge cycles 800 times, CuMn₂O₄/Mn_xO_yThe specific discharge capacity of composite material from 153.3F/g is reduced to 134.4F/g, and the capacity retention ratio of material is initial 88% after 800 charge and discharge cycles； Under the current density of 0.8A/g after charge and discharge cycles 600 times, CuMn₂O₄/Mn_xO_yThe specific discharge capacity of composite material from 133.3F/g is reduced to 120.9F/g, and the capacity retention ratio of material is initial 91% after 600 charge and discharge cycles. It can be seen that after it have passed through multiple charge and discharge cycles by the impedance curve of material before and after comparison charge and discharge, the impedance of the material Increase seldom, material keeps good high rate performance and cycle performance.

Detailed description of the invention

Fig. 1 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yThe preparation method flow chart of composite material；

Fig. 2 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yThe electrochemical property test method flow diagram of material；

Fig. 3 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yThe XRD diagram of composite material；

Fig. 4 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yThe SEM of composite material schemes；

Fig. 5 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yCyclic voltammetric of the composite material under different scanning rates Curve；

Fig. 6 is the specific capacity schematic diagram of CV curve under different scanning rates provided in an embodiment of the present invention；

Fig. 7 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yHead of the composite material under different charging and discharging currents density Secondary charging and discharging curve figure；

Fig. 8 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yElectric discharge specific volume of the composite material under different current densities Spirogram；

Fig. 9 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yCharge and discharge of the composite material under different current densities follow Ring figure；

Figure 10 (a) is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yComposite material recycles under 0.2A/g current density 800 specific capacities and efficiency charts；

Figure 10 (b) is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yComposite material recycles under 0.8A/g current density 600 specific capacities and efficiency charts；

Figure 11 is CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yAC impedance of the composite material before and after charge and discharge.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.

Application principle of the invention is described in detail with reference to the accompanying drawing.

As shown in Figure 1, CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yComposite material the preparation method comprises the following steps:

S101: by KOH and NaOH deionized water dissolving, wiring solution-forming A；

S102: by the Cu (CH of 0.5mol/L₃COO)₂Solution pours into the Mn (CH of 1.0mol/L₃COO)₂It is made into solution molten Liquid B；

S103: under agitation, solution B is added dropwise in solution A；

S104: after being added dropwise to complete, mixed solution is transferred in the autoclave of polytetrafluoroethyllining lining, at 180 DEG C Under the conditions of react for 24 hours, product is centrifugated after cooled to room temperature；

S105: the substance after separation being placed in tube furnace and is dried, and 500 DEG C of calcining 5h, naturally cold in air atmosphere But.

In step s101 by 3.00gKOH and 1.50gNaOH 20mL deionized water dissolving, wiring solution-forming A.

In step s 102 by the Cu (CH of 5mL0.5mol/L₃COO)₂Solution pours into the Mn (CH of 5mL1.0mol/L₃COO)₂ Wiring solution-forming B in solution.

CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yThe physical property of composite material is tested by XRD and SEM Characterization, XRD test use Empyrean x-ray diffractometer, and pipe presses 40kV, the Cu target K of Guan Liu 40mA, λ=0.15406nm_α Ray；SEM test uses acceleration voltage for the JSM-6360LV scanning electron microscope of 25kV.

CuMn provided in an embodiment of the present invention₂O₄/Mn_xO_yThe electrochemical property test method of material are as follows:

S201: with the CuMn of preparation₂O₄/Mn_xO_yMaterial as a positive electrode active material, make as conductive agent, PTFE by acetylene black For binder, it is uniformly mixed according to the ratio of mass ratio 8:1:1, anode electrode piece is made；

S202: using capacitor active carbon as negative electrode active material, acetylene black is as conductive agent, and PTFE is as binder, together Sample is uniformly mixed according to the ratio of mass ratio 8:1:1, and negative electricity pole piece is made；

S203: to be saturated KNO₃Solution is assembled into water system button cell as electrolyte；

S204: using the prepared button cell of LANHE battery test system measurement, electrochemical workstation measurement circulation volt Pacify the AC impedance of curve and material before and after charge and discharge.

The invention will be further described combined with specific embodiments below.

XRD analysis

The material is CuMn as can be seen from Figure 3₂O₄/Mn_xO_yComposite material, 111,220 (30 °), 311,222 in XRD diagram (37 °), 400 (44 °), 422,511,440 (63 °), peak and standard card PDF#01-084-0543 corresponding to 533 match, It is CuMn₂O₄Diffraction maximum；211,222 (33 °), 400 (38 °), 332,134,440 (55 °), peak and mark corresponding to 611,622 Quasi- card PDF#01-089-4836 matches, and is Mn₂O₃Diffraction maximum；110, peak corresponding to 200,310,301,451,312 Match with standard card PDF#01-072-1982, is MnO₂Diffraction maximum；Other peaks are Mn₃O₄Corresponding peak.In figure The peak shape at each peak is sharp, and without other miscellaneous peaks.

Sem analysis

As can be seen from Figure 4 prepared CuMn₂O₄/Mn_xO_yComposite material has many random little particles to reunite It is attached on hexagon disk together.Presoma was synthesized by hydro-thermal method before this in the preparation process of material, further through high temperature Calcining has obtained final product.Due to there is hot stage during the preparation process, so having agglomeration.

Electrochemical property test

Fig. 5 is CuMn₂O₄/Mn_xO_yThe CV curve that composite material measures under different scanning rates.Fig. 6 is different scanning speed The specific capacity of CV curve under rate, can calculate according to the following formula 1mV/s, 3mV/s, 5mV/s, 10mV/s, 30mV/s, Specific capacity under 50mV/s, 100mV/s sweep speed be respectively 196.9F/g, 167.9F/g, 146.5F/g, 128.2F/g, 109.9F/g、100.7F/g、82.4F/g。

Wherein C is specific capacity；Q is discharge electricity amount, i.e. the ratio between the half Yu sweep speed of CV curve integral area；M is to live The quality of property substance；Δ V is potential region.

Fig. 7 is CuMn₂O₄/Mn_xO_yFirst charge-discharge curve graph of the composite material under different charging and discharging currents density；Fig. 8 It is CuMn₂O₄/Mn_xO_ySpecific discharge capacity figure of the composite material under different current densities.It can be seen from Fig. 7 and Fig. 8 Specific discharge capacity under 0.1A/g, 0.2A/g, 0.4A/g, 0.8A/g, 1.0A/g, 2.0A/g, 4.0A/g current density is respectively 164.6F/g,151.7F/g,141.7F/g,131.1F/g,127.0F/g,113.1F/g,94.9F/g.Charge-discharge test measures Data compared with the data that CV curve is calculated, it can be found that the size of specific capacity very close to.

Fig. 9 is CuMn₂O₄/Mn_xO_yCharge and discharge cycles figure of the composite material under different current densities.It can from figure Out with the increase of current density, the specific capacity of material is sequentially reduced.And specific capacity and Fig. 7, Fig. 8 survey under each multiplying power The data obtained are consistent.As can be seen from the figure the material has good high rate performance.

Figure 10 is CuMn₂O₄/Mn_xO_yThe cycle performance figure of composite material.It can find out from Figure 10 (a) 0.2A/g's Under current density after charge and discharge cycles 800 times, CuMn₂O₄/Mn_xO_yThe specific discharge capacity of composite material is dropped from 153.3F/g As low as 134.4F/g, the capacity retention ratio of material is initial 88% after 800 charge and discharge cycles.It can be from Figure 10 (b) after finding out under the current density of 0.8A/g charge and discharge cycles 600 times in, CuMn₂O₄/Mn_xO_yThe electric discharge of composite material Specific capacity is reduced to 120.9F/g from 133.3F/g, and the capacity retention ratio of material is first after 600 charge and discharge cycles 91% to begin.

Figure 11 is CuMn₂O₄/Mn_xO_yAC impedance curve of the composite material before and after charge and discharge compares EIS figure medium-high frequency The semicircle diameter in area and the straight slope of low frequency range, it can be seen that after it have passed through multiple charge and discharge cycles, CuMn₂O₄/Mn_xO_yThe impedance of composite material increases.It can be seen that the stability of the material is not very well, by repeatedly filling The structure of material may change after discharge cycles, so impedance can become larger.

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (5)

1. a kind of CuMn₂O₄/Mn_xO_yThe preparation method of composite material, which is characterized in that the CuMn₂O₄/Mn_xO_yComposite material The preparation method comprises the following steps:

Step 1: by 3.00gKOH and 1.50gNaOH 20mL deionized water dissolving, wiring solution-forming A；

Step 2: by the Cu (CH of 5mL0.5mol/L₃COO)₂Solution pours into the Mn (CH of 5mL1.0mol/L₃COO)₂It is made into solution Solution B；

Step 3: under agitation, solution B is added dropwise in solution A；

Step 4: after being added dropwise to complete, mixed solution being transferred in the autoclave of polytetrafluoroethyllining lining, in 180 DEG C of items It reacts under part for 24 hours, is centrifugated product after cooled to room temperature；

Step 5: the substance after separation being placed in tube furnace and is dried, in air atmosphere 500 DEG C of calcining 5h, natural cooling ?.

2. CuMn as described in claim 1₂O₄/Mn_xO_yThe preparation method of composite material, which is characterized in that the CuMn₂O₄/ Mn_xO_yThe physical property of composite material carries out test characterization by XRD and SEM, and XRD test uses Empyrean X-ray diffraction Instrument, pipe press 40kV, the Cu target K of Guan Liu 40mA, λ=0.15406nm_αRay；SEM test uses acceleration voltage for the JSM- of 25kV 6360LV scanning electron microscope.

3. one kind CuMn as described in claim 1~2 any one₂O₄/Mn_xO_yThe preparation method preparation of composite material CuMn₂O₄/Mn_xO_yComposite material.

4. a kind of CuMn as claimed in claim 3₂O₄/Mn_xO_yThe test method of the chemical property of composite material, feature exist In the CuMn₂O₄/Mn_xO_yThe electrochemical property test method of material are as follows:

Step 1: with the CuMn of preparation₂O₄/Mn_xO_yAs a positive electrode active material, acetylene black is as conductive agent, PTFE conduct for material Binder is uniformly mixed according to the ratio of mass ratio 8:1:1, anode electrode piece is made；

Step 2: using capacitor active carbon as negative electrode active material, acetylene black is as conductive agent, and PTFE is as binder, equally It is uniformly mixed according to the ratio of mass ratio 8:1:1, negative electricity pole piece is made；

Step 3: to be saturated KNO₃Solution is assembled into water system button cell as electrolyte；

Step 4: using the prepared button cell of LANHE battery test system measurement, electrochemical workstation measures cyclic voltammetric The AC impedance of curve and material before and after charge and discharge.

5. one kind CuMn as described in claim 3₂O₄/Mn_xO_yThe supercapacitor of composite material preparation.