Cement-based high-entropy electrolyte, preparation method thereof and cement-based supercapacitor

Abstract

This invention discloses a cement-based high-entropy electrolyte, its preparation method, and a cement-based supercapacitor. The general formula of the cement-based high-entropy electrolyte is A. a C b M c Cl d In the formula, A is a mixture of CaO, SiO2, Al2O3, Fe2O3, and MgO; M includes five or more metallic elements from groups IA, IIA, IVB, VIB, VIIB, VIII, IB, IIB, and IIIA; 1 < a < 5, 0.05 < b < 1, 0.001 < c < 0.02, and 0.01 < d < 0.2. First, weigh the cement matrix A according to the stoichiometric ratio of the general formula. a Toner C b and metal chloride M c Cl d After ball milling, the mixture is thoroughly stirred with a sucrose solution. The mixture is then poured into a mold, and two electrodes are inserted parallel and vertically into both sides of the electrolyte. The mixture is vibrated to remove air, cured for 28 days, and then demolded to obtain a cement-based high-entropy electrolyte supercapacitor. This method introduces the concept of high entropy into cement-based electrolytes, controlling the capacitance, cycle life, and cycle stability of the cement-based supercapacitor by adjusting the material ratio of the high-entropy electrolyte.

Description

Technical Field

[0001] This invention relates to the field of supercapacitor fabrication technology, specifically to a cement-based high-entropy electrolyte, its preparation method, and a cement-based supercapacitor. Background Technology

[0002] High-entropy alloys are a novel material concept that breaks with the previously held view that multi-principal elements cannot form a single phase. "High-entropy oxides," "high-entropy borides," and "high-entropy sulfides," among others, have been applied to various fields of materials science due to their high-entropy effect, cocktail effect, lattice distortion effect, and hysteresis diffusion effect.

[0003] In recent years, cement-based supercapacitors have gradually emerged among various types of supercapacitors due to their certain capacitance storage capacity, and are considered a large-scale building energy storage device with great potential. However, problems such as low capacitance and poor cycle stability still exist, which greatly limit their further application.

[0004] Developing cement-based high-entropy electrolytes for cement-based supercapacitors by leveraging the many superior properties of high-entropy materials improves the ionic conductivity of the electrolyte, expands the capacitance of supercapacitors, and extends the cycle life of capacitors. This aligns with the current development goals of cement-based supercapacitors, maximizes energy storage efficiency, and reduces energy storage costs. Summary of the Invention

[0005] One of the objectives of this invention is to provide a cement-based high-entropy electrolyte to overcome the problems of low capacity, short cycle life, and poor cycle stability of existing cement-based electrolytes.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A cement-based high-entropy electrolyte, wherein the general formula of the cement-based high-entropy electrolyte is A. a C b M c Cl d In the formula, A is a mixture of CaO, SiO2, Al2O3, Fe2O3, and MgO; M includes five or more metallic elements from groups IA, IIA, IVB, VIB, VIIB, VIII, IB, IIB, and IIIA; 1 < a < 5, 0.05 < b < 1, 0.001 < c < 0.02, and 0.01 < d < 0.2.

[0008] Preferably, by mass percentage, A contains 62-67% CaO, 20-24% SiO2, 4-7% Al2O3, 2.5-6% Fe2O3, and the remainder is MgO; The M includes five or more metallic elements selected from Li, Na, K, Mg, Ca, Ba, Cr, Mn, Fe, Co, Cu, Zn, and Al, with each element having the same atomic ratio.

[0009] Preferably, a=3.98, b=0.83, 0.003<c<0.09, 0.05<d<0.15.

[0010] Preferably, the chemical formula of the cement-based high-entropy electrolyte is Ca. 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.005 Na 0.005 K 0.005 Ba 0.005 Cr 0.005 Mn 0.005 Cl 0.05 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.01 Na 0.0 1K 0.01 Ba 0.01 Cr 0.01 Mn 0.01 Cl 0.1 , or Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.015 Na 0.015 K 0.015 Ba 0.015 Cr 0.015 Mn 0.015 Cl 0.15 .

[0011] A second objective of this invention is to provide a method for preparing a cement-based high-entropy electrolyte, comprising the following steps: 1) Weigh cement matrix A according to the stoichiometric ratio of the general formula. a Toner C b and metal chloride M c Cl d They are placed together in a ball mill to obtain a mixed powder; 2) By mass percentage, mix 40-65% of the mixed powder obtained in step 1) with 35-60% of the sucrose solution thoroughly until homogeneous.

[0012] Preferably, the ball mill in step 1) has a rotation speed of 300-800 rpm and a ball milling time of 5-20 hours.

[0013] Preferably, the concentration of the sucrose solution in step 2) is 0.001-0.005%.

[0014] A cement-based supercapacitor uses the aforementioned cement-based high-entropy electrolyte as the electrolyte.

[0015] The electrodes of the capacitor are one of copper mesh, aluminum mesh, nickel mesh, copper foam, aluminum foam, or nickel foam.

[0016] A method for preparing a cement-based supercapacitor involves injecting a cement-based high-entropy electrolyte into a mold, inserting two electrodes parallel and vertically into both sides of the cement-based high-entropy electrolyte, placing the mold on a vibration table to expel gas, placing it in a curing chamber for 28 days, and then demolding it to obtain a cement-based high-entropy electrolyte supercapacitor.

[0017] Preferably, the curing conditions of the curing box are a temperature of 25±5℃ and a relative humidity of 90±5%.

[0018] Compared with the prior art, the beneficial effects of the present invention are: 1) The method of this invention introduces the concept of high entropy into cement-based electrolytes, and the capacitance, cycle life and cycle stability of cement-based supercapacitors can be controlled by adjusting the material ratio of the high entropy electrolyte; 2) The high entropy effect brought about by multiple metal chlorides generates a large number of pore structures in the cement matrix. The pores provide a place for ion conduction, improve ion conductivity, and thus effectively improve the electrochemical performance of cement-based supercapacitors. 3) The raw materials used in this invention to prepare high-entropy electrolytes are inexpensive, the preparation process is simple and easy to implement, and stable products can be obtained, which broadens the prospects for the early realization of "energy storage / building integration" of cement-based supercapacitors. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0020] Figure 1The time-voltage curve of the cement-based high-entropy electrolyte supercapacitor prepared in Example 1.

[0021] Figure 2 The time-voltage curve of the cement-based high-entropy electrolyte supercapacitor prepared in Example 2.

[0022] Figure 3 The time-voltage curve of the cement-based high-entropy electrolyte supercapacitor prepared in Example 3.

[0023] Figure 4 The time-voltage curve of the cement-based high-entropy electrolyte supercapacitor prepared in Example 4.

[0024] Figure 5 The time-voltage curve of the cement-based high-entropy electrolyte supercapacitor prepared in Example 5. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] Example 1 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.005 Na 0.005 K 0.005 Ba 0.005 Cr 0.005 Mn 0.005 Cl 0.05 The preparation steps for a cement-based supercapacitor using a cement-based high-entropy electrolyte are as follows: Weigh out 60g CaO, 20g SiO2, 8g Al2O3, 8g Fe2O3, 4g MgO, 10g carbon powder, 0.21g LiCl, 0.29g NaCl, 0.37g KCl, 1.04g BaCl2, 0.79g CrCl3, and 0.63g MnCl2. Place all the above materials together in a ball mill and ball mill at 500 rpm for 10 hours. Pass the mixture through a 200-mesh sieve to obtain a mixed powder. Thoroughly stir the mixed powder with 60mL of 0.001% sucrose solution. After mixing evenly, pour the mixture into a mold. Insert two copper mesh electrodes into the mold, parallel and vertically respectively. First, place the mold on a vibration table to remove gas, then place it in a curing chamber for 28 days. The curing conditions in the curing chamber are 25±5℃ and 90±5% relative humidity. Demold the mold to obtain a cement-based high-entropy electrolyte supercapacitor.

[0027] The cement-based high-entropy electrolyte supercapacitor prepared in this embodiment operates at a current density of 1 mA / cm². 2 Under the specified conditions, a charge-discharge test was conducted, and its specific capacitance was 116.40 mF / cm². 3 The decay rate after 100 charge-discharge cycles is 10.81%.

[0028] Example 2 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.01 Na 0.01 K 0.01 Ba 0.01 Cr 0.01 Mn 0.01 Cl 0.1 The preparation steps for a cement-based supercapacitor using a cement-based high-entropy electrolyte are as follows: Weigh out 60g CaO, 20g SiO2, 8g Al2O3, 8g Fe2O3, 4g MgO, 10g carbon powder, 0.42g LiCl, 0.58g NaCl, 0.74g KCl, 2.08g BaCl2, 1.58g CrCl3, and 1.26g MnCl2. Place all the above materials together in a ball mill and ball mill at 500 rpm for 10 hours. Pass the mixture through a 200-mesh sieve to obtain a mixed powder. Thoroughly stir the mixed powder with 60mL of 0.001% sucrose solution. After mixing evenly, pour the mixture into a mold. Insert two copper mesh electrodes into the mold, parallel and vertically respectively. First, place the mold on a vibration table to remove gas, then place it in a curing chamber for 28 days. The curing conditions in the curing chamber are 25±5℃ and 90±5% relative humidity. Demold the mold to obtain a cement-based high-entropy electrolyte supercapacitor.

[0029] The cement-based high-entropy electrolyte supercapacitor prepared in this embodiment operates at a current density of 1 mA / cm². 2 Under the specified conditions, a charge-discharge test was conducted, and its specific capacitance was 176.13 mF / cm². 3 The decay rate after 100 charge-discharge cycles is 8.61%.

[0030] Example 3 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.015 Na 0.015 K 0.015 Ba 0.015 Cr 0.015 Mn 0.015 Cl 0.15 The preparation steps for a cement-based supercapacitor using a cement-based high-entropy electrolyte are as follows: Weigh out 60g CaO, 20g SiO2, 8g Al2O3, 8g Fe2O3, 4g MgO, 10g carbon powder, 0.63g LiCl, 0.87g NaCl, 1.11g KCl, 3.12g BaCl2, 2.37g CrCl3, and 1.89g MnCl2. Place all the above materials together in a ball mill and ball mill at 500 rpm for 10 hours. Pass the mixture through a 200-mesh sieve to obtain a mixed powder. Thoroughly stir the mixed powder with 60mL of 0.001% sucrose solution. After mixing evenly, pour the mixture into a mold. Insert two copper mesh electrodes into the mold, parallel and vertically respectively. First, place the mold on a vibration table to remove gas, then place it in a curing chamber for 28 days. The curing conditions in the curing chamber are 25±5℃ and 90±5% relative humidity. Demold the mold to obtain a cement-based high-entropy electrolyte supercapacitor.

[0031] The cement-based high-entropy electrolyte supercapacitor prepared in this embodiment operates at a current density of 1 mA / cm². 2 Under the specified conditions, a charge-discharge test was conducted, and its specific capacitance was 291.00 mF / cm². 3 The decay rate after 100 charge-discharge cycles is 5.81%.

[0032] Example 4 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 K 0.005Ba 0.005 Cr 0.005 Mn 0.005 Fe 0.005 Zn 0.005 Cl 0.06 The preparation steps for a cement-based supercapacitor using a cement-based high-entropy electrolyte are as follows: Weigh out 60g CaO, 20g SiO2, 8g Al2O3, 8g Fe2O3, 4g MgO, 10g carbon powder, 0.37g KCl, 1.04g BaCl2, 0.79g CrCl3, 0.63g MnCl2, 0.64g FeCl2, and 0.68g ZnCl2. Place all the above materials together in a ball mill and ball mill at 500 rpm for 10 hours. Pass the mixture through a 200-mesh sieve to obtain a mixed powder. Thoroughly stir the mixed powder with 60mL of 0.001% sucrose solution. After mixing evenly, pour the mixture into a mold. Insert two copper mesh electrodes into the mold, parallel and vertically respectively. First, place the mold on a vibration table to remove gas, then place it in a curing chamber for 28 days. The curing conditions in the curing chamber are 25±5℃ and 90±5% relative humidity. Demold the mold to obtain a cement-based high-entropy electrolyte supercapacitor.

[0033] The cement-based high-entropy electrolyte supercapacitor prepared in this embodiment operates at a current density of 1 mA / cm². 2 Under the specified conditions, a charge-discharge test was conducted, and its specific capacitance was 321.63 mF / cm². 3 The decay rate after 100 charge-discharge cycles is 3.22%.

[0034] Example 5 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 K 0.005 Mg 0.005 Ca 0.005 Co 0.005 Cu 0.005 Al 0.005 Cl 0.06 The preparation steps for a cement-based supercapacitor using a cement-based high-entropy electrolyte are as follows: Weigh out 60g CaO, 20g SiO2, 8g Al2O3, 8g Fe2O3, 4g MgO, 10g carbon powder, 0.37g KCl, 0.48g MgCl2, 0.56g CaCl2, 0.65g CoCl2, 0.67g CuCl2, and 0.67g AlCl3. Place all the above materials together in a ball mill and ball mill at 500 rpm for 10 hours. Pass the mixture through a 200-mesh sieve to obtain a mixed powder. Thoroughly stir the mixed powder with 60mL of 0.001% sucrose solution. After mixing evenly, pour the mixture into a mold. Insert two copper mesh electrodes into the mold, parallel and vertically respectively. First, place the mold on a vibration table to remove gas, then place it in a curing chamber for 28 days. The curing conditions in the curing chamber are 25±5℃ and 90±5% relative humidity. Demold the mold to obtain a cement-based high-entropy electrolyte supercapacitor.

[0035] The cement-based high-entropy electrolyte supercapacitor prepared in this embodiment operates at a current density of 1 mA / cm². 2 Under the specified conditions, a charge-discharge test was conducted, and its specific capacitance was 90.30 mF / cm². 3 The decay rate after 100 charge-discharge cycles is 15.76%.

[0036] Figure 1-5 The time-voltage curves for Examples 1-5 are shown below. According to formula (1), the longer the discharge time, the larger the volumetric capacitance of the cement-based high-entropy electrolyte supercapacitor. The calculated volumetric capacitances for Examples 1-5 are 116.40, 176.13, 291.00, and 321.63 mF / cm², respectively. 3 and 90.30mF / cm 3 .

[0037] (1) In the formula, C is the volumetric capacitance (mF / cm²). 3 i—Discharge current density (mA / cm²) 2 Δt—discharge time (s); ΔV—voltage (V); V—electrolyte volume (cm³) 3 ).

[0038] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. For the apparatus disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the description is relatively simple; relevant parts can be referred to the method section.

[0039] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A cement-based high-entropy electrolyte, characterized in that, The general formula for this cement-based high-entropy electrolyte is A. a C b M c Cl d In the formula, A is a mixture of CaO, SiO2, Al2O3, Fe2O3, and MgO; M includes five or more metallic elements from groups IA, IIA, IVB, VIB, VIIB, VIII, IB, IIB, and IIIA. 1<a<5, 0.05<b<1, 0.001<c<0.02, 0.01<d<0.

2.

2. The cement-based high-entropy electrolyte according to claim 1, characterized in that, By mass percentage, A contains 62-67% CaO, 20-24% SiO2, 4-7% Al2O3, 2.5-6% Fe2O3, and the remainder is MgO. The M includes five or more metallic elements selected from Li, Na, K, Mg, Ca, Ba, Cr, Mn, Fe, Co, Cu, Zn, and Al, with each element having the same atomic ratio.

3. The cement-based high-entropy electrolyte according to claim 2, characterized in that, a=3.98, b=0.83, 0.003<c<0.09, 0.05<d<0.

15.

4. The cement-based high-entropy electrolyte according to claim 1, characterized in that, The chemical formula of the cement-based high-entropy electrolyte is Ca. 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.005 Na 0.005 K 0.005 Ba 0.005 Cr 0.005 Mn 0.005 Cl 0.05 Ca 1.07 Si 0.33 Al 0.16 Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.01 Na 0.01 K 0.01 Ba 0.01 Cr 0.01 Mn 0.01 Cl 0.1 , or Ca 1.07 Si 0.33 Al 0.1 6Fe 0.1 Mg 0.1 O 2.22 C 0.83 Li 0.015 Na 0.015 K 0.015 Ba 0.015 Cr 0.015 Mn 0.015 Cl 0.15 .

5. A method for preparing a cement-based high-entropy electrolyte according to any one of claims 1 to 4, characterized in that, Includes the following steps: 1) Weigh cement matrix A according to the stoichiometric ratio of the general formula. a Toner C b and metal chloride M c Cl d They are placed together in a ball mill to obtain a mixed powder; 2) By mass percentage, mix 40-65% of the mixed powder obtained in step 1) with 35-60% of the sucrose solution thoroughly until homogeneous.

6. The method for preparing a cement-based high-entropy electrolyte according to claim 5, characterized in that, Step 1) The ball mill speed is 300-800 rpm, and the ball milling time is 5-20 hours.

7. A method for preparing a cement-based high-entropy electrolyte according to any one of claims 1 to 4, characterized in that, Step 2) The concentration of the sucrose solution is 0.001-0.005%.

8. A cement-based supercapacitor, characterized in that, The cement-based high-entropy electrolyte described in any one of claims 1 to 4 is used as the electrolyte.

9. A cement-based supercapacitor according to claim 8, characterized in that, The electrodes of the capacitor are one of copper mesh, aluminum mesh, nickel mesh, copper foam, aluminum foam, or nickel foam.

10. A method for preparing a cement-based supercapacitor according to claim 8 or 9, characterized in that, The cement-based high-entropy electrolyte is injected into a mold, and two electrodes are inserted into the cement-based high-entropy electrolyte in parallel and vertical positions on both sides. The mold is placed on a vibration table to expel the gas, and then placed in a curing chamber for 28 days. After demolding, the cement-based high-entropy electrolyte supercapacitor is obtained.

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