CN108134089B - High-load active material electrode and preparation and application thereof - Google Patents

High-load active material electrode and preparation and application thereof Download PDF

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CN108134089B
CN108134089B CN201611088186.6A CN201611088186A CN108134089B CN 108134089 B CN108134089 B CN 108134089B CN 201611088186 A CN201611088186 A CN 201611088186A CN 108134089 B CN108134089 B CN 108134089B
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electrode
pore
forming agent
active material
binder
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张华民
郑琼
易红明
刘婉秋
张洪章
冯凯
李先锋
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a method for preparing a high-load active material electrode, which is characterized in that a pore-forming agent is added in the preparation process of electrode slurry, the electrode slurry is coated on an aluminum foil current collector in a blade mode through coating equipment to form an electrode-current collector integrated electrode, and in the drying process, the pore-forming agent is heated and decomposed and volatilizes in a gas mode, so that the electrode structure is fluffy and a large number of hole structures are formed. The high-load electrode with the fluffy porous structure prepared by the method can effectively promote the diffusion and mass transfer of sodium ions in the electrode, and particularly strengthen the diffusion of the sodium ions in the electrode under high magnification. Through battery performance tests, the performance of the sodium ion battery assembled by the electrode prepared by the pore-forming agent and prepared by the high-load active substance is greatly improved, and particularly the performance is remarkably improved under high multiplying power.

Description

High-load active material electrode and preparation and application thereof
Technical Field
The invention relates to the technical field of electrode materials of sodium-ion batteries, in particular to a method for preparing a high-load active substance electrode by adopting a pore-forming agent and application of the high-load active substance electrode in a sodium-ion battery.
Background
As is well known, lithium ion batteries have advantages of small size, light weight, high energy density, and the like, and are playing an increasingly important role in portable devices such as mobile phones and notebook computers, and vehicles such as electric bicycles and electric automobiles. The amount of lithium ion batteries is increasing year by year, and particularly energy storage batteries supporting the development of new energy sources are in great demand. According to the data of the U.S. geological survey, the amount of lithium resources (metallic lithium equivalent) that has been globally explored in 2015 is 3950 million tons, with almost 73% being centrally distributed in south america in a few countries. The worldwide exploitable lithium resource reserve is about 1350 ten thousand tons (about 7100 ten thousand tons calculated by lithium carbonate equivalent), the annual average exploitation amount of the lithium resource in recent two years is 3.5 ten thousand tons, and even if the annual exploitation amount of the lithium resource is predicted to be only 385 years, and the annual exploitation amount of the lithium resource is gradually increased at present. With the rapid expansion of the application range of lithium ion batteries, the situation of short supply and short demand of lithium resources inevitably occurs. Therefore, the task of seeking a lithium resource which is abundant in reserves, low in cost and capable of replacing a lithium ion battery is urgent.
According to the abundance data of various chemical elements in the earth crust, the storage capacity of the metal sodium element is 2.75 percent and is about 400 times of the lithium content; and the metallic sodium distribution area is wide (sodium is distributed all over the world, while about 70% of lithium is concentrated in south america); meanwhile, the physicochemical properties and the releasing/inserting mechanisms of sodium and lithium are similar, so that the research and development of the sodium-ion battery are expected to relieve the problem of limited development of the energy storage battery caused by the shortage of lithium resources to a certain extent. However, since the radius of sodium ions is larger than that of lithium ions, the energy density and power density are lower than those of lithium ion batteries. However, the energy density requirements of batteries are not too high in large-scale energy storage applications, and cost and lifetime are important concerns. From this perspective, sodium ion batteries have a greater market competitive advantage over lithium ion batteries in large scale energy storage applications. Therefore, the technology of the sodium ion battery for the large-scale energy storage application is vigorously developed and has very important strategic significance.
Research and development of a sodium ion battery with low price and excellent performance are the key points for realizing the practicability of the sodium ion battery. At present, the loading of active substances on the electrode of a sodium ion battery is lower (1-2 mg cm)-2) Although battery performance is significantly improved by various methods, batteries assembled with low-load active material electrodes still cannot meet practical application requirements. High loading of active substancesThe preparation of the electrode is the key to the practical development of the sodium ion battery. The increase of the loading of active substances inevitably causes the mass transfer of sodium ions in the electrode to be blocked, and the overall performance of the battery is reduced, particularly the performance of the battery under high multiplying power is reduced. Therefore, it is very key to explore an electrode preparation method which is beneficial to improving the sodium ion diffusion mass transfer in the electrode with high loading of active substances.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the following specific technical scheme:
provides a method for preparing a high-load active material electrode by adopting a pore-forming agent and is applied to a sodium ion battery.
1) Firstly, mixing an electrode active substance, a conductive agent and a binder into a solute, and dissolving the solute by using a solvent N-methylpyrrolidone, wherein the solute is 20-50% of the total mass of the solvent and the solute; meanwhile, dissolving a pore-forming agent in a solvent N-methyl pyrrolidone, wherein the pore-forming agent accounts for 20-50% of the total mass of the solvent and the pore-forming agent; the mixing mass ratio of the electrode active substance, the conductive agent and the binder is 50-90: 5-20: 5-30; mixing the dissolved electrode active substance, the conductive agent, the binder and the dissolved pore-forming agent, and stirring for 4-6h on a stirrer to form uniformly mixed thick slurry in a black state;
2) coating the slurry on an aluminum foil to obtain an electrode-current collector integrated electrode; the supporting amount of the electrode active material is controlled by the thickness of the electrode coated on the aluminum foil; the thickness of the coated electrode is 400-2000 μm, and the obtained electrode active material supporting amount is 5-30mg/cm2；
3) And (3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 70-100 ℃ for drying for 12-24 h.
The electrode active material in the step 1) is used as a positive electrode material or a negative electrode material, and the positive electrode material is one or more than two of an oxide, a polyanion compound and a Prussian blue compound; the negative electrode material is one or more than two of carbon-based material, alloy material and phosphate.
The conductive agent in the step 1) is one or more than two of Super P, carbon black, reduced graphene oxide, Ketjen black and acetylene black carbon materials; the binder is one or more than two of PVDF, PVDF-HFP and PTFE; the pore-forming agent is one or more of 2, 4, 6-trinitrotoluene, carbon powder, polyvinyl alcohol (PVA), polyethylene glycol (PEG), starch, PMMA, ammonium bicarbonate, urea and polyvidone (PVP).
The pore-forming agent is 1-10% of the total mass of the electrode active substance, the conductive agent and the binder. The oxide is NaCoO2、NaMnO2、NaFeO2、NaxFe0.5Mn0.5O2、NaNi0.5Mn0.5O2、Na2/3Ni1/3Mn2/3O2、NaNi1/3Mn1/3Co1/ 3O2、NaNi1/3Fe1/3Mn1/3O2、Na0.44MnO2One of (1); the polyanionic compound is NaFePO4、Na2FeP2O7、Na4Fe3(PO4)2P2O7、Na3V2(PO4)3、Na3NiZr（PO4)3、Na3V2(PO4)2F3、Na2FePO4F、Na2FeSiO4One of (1); the Prussian blue compound is Na4Fe(CN)6、Na1.72MnFe(CN)6One kind of (1).
The carbon-based material is one of graphene, hard carbon and soft carbon; the alloy material is one of Sb/C, SnSb/C and Sn/C; the phosphate is Na3V2(PO4)3、 NaTi2(PO4)3And Na3MnTi（PO4）3One kind of (1).
And stamping the dried integrated electrode into a wafer electrode with the diameter of 14mm, assembling the wafer electrode into the sodium ion battery, and realizing the application of the prepared high-load active substance electrode in the sodium ion battery.
The invention has the advantages of
The invention provides a method for preparing a high-load active material electrode by adopting a pore-forming agent. The high-load electrode with the fluffy porous structure prepared by the method can effectively promote the diffusion and mass transfer of sodium ions in the electrode, particularly strengthen the diffusion of the sodium ions in the electrode under high multiplying power, and is beneficial to improving the performance of a sodium ion battery with the high-load electrode, particularly the battery under the high multiplying power.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a high-loading active material electrode using a pore-forming agent;
FIG. 2 is a graph comparing the rate performance of example 1 and comparative example;
FIG. 3 is a graph comparing the rate performance of example 2 and comparative example;
FIG. 4 is a graph comparing the rate performance of example 3 with that of a comparative example;
FIG. 5 is a graph comparing the rate performance of example 4 and comparative example.
Detailed Description
Example 1: (at 2.5% NH)4H2CO3Is a pore-forming agent)
Electrode active material (positive electrode material is selected from sodium vanadium phosphate, 0.35 g), conductive agent (Super P, 0.1 g) and binder (PVDF, 0.05 g) are mixed according to the mass ratio of 70%: 20%: 10% were mixed and dissolved in 1.3g of N-methylpyrrolidone solvent; 0.0125g (2.5%) of pore-forming agent NH is added simultaneously4H2CO3Dissolved in 0.04g of N-methylpyrrolidone solvent. Dissolving electrode active material, conductive agent, binding agent and dissolved pore-forming agent NH4H2CO3And (4) mixing, namely stirring on a stirrer for 5 hours to form uniformly mixed black viscous slurry. And uniformly coating the slurry on the aluminum foil by adopting coating equipment to obtain the electrode-current collector integrated electrode. The thickness of the coated electrode was 1000. mu.And m is selected. And (3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 100 ℃ for drying for 12 h. Punching the dried integrated electrode into a wafer electrode with the diameter of 14mm, taking the wafer electrode as a positive electrode, taking a metal sodium sheet as a negative electrode, and taking 1M NaClO as a negative electrode4(the volume ratio of Ethylene Carbonate (EC)/diethyl carbonate (DEC) is 1:1 and 2 wt.% FEC) is used as electrolyte, and a sodium ion battery is assembled. The active material loading of the assembled sodium-ion battery is about 15mg cm-2。
Example 2: (at 5% NH)4H2CO3Is a pore-forming agent)
Electrode active material (positive electrode material is selected from sodium vanadium phosphate, 0.35 g), conductive agent (Super P, 0.1 g) and binder (PVDF, 0.05 g) are mixed according to the mass ratio of 70%: 20%: 10% were mixed and dissolved in 1.3g of N-methylpyrrolidone solvent; while 0.025g (5%) of a pore-forming agent NH was added4H2CO3Dissolved in 0.04g of N-methylpyrrolidone solvent. Dissolving electrode active material, conductive agent, binding agent and dissolved pore-forming agent NH4H2CO3And (4) mixing, namely stirring on a stirrer for 5 hours to form uniformly mixed black viscous slurry. And uniformly coating the slurry on the aluminum foil by adopting coating equipment to obtain the electrode-current collector integrated electrode. The thickness of the coated electrode was 1000. mu.m. And (3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 100 ℃ for drying for 12 h. Punching the dried integrated electrode into a wafer electrode with the diameter of 14mm, taking the wafer electrode as a positive electrode, taking a metal sodium sheet as a negative electrode, and taking 1M NaClO as a negative electrode4(the volume ratio of Ethylene Carbonate (EC)/diethyl carbonate (DEC) is 1:1 and 2 wt.% FEC) is used as electrolyte, and a sodium ion battery is assembled. The active material loading of the assembled sodium-ion battery is about 15mg cm-2。
Example 3: (2.5% polyethylene glycol as pore-forming agent)
Electrode active material (positive electrode material is selected from sodium vanadium phosphate, 0.35 g), conductive agent (Super P, 0.1 g) and binder (PVDF, 0.05 g) are mixed according to the mass ratio of 70%: 20%: 10% were mixed and dissolved with 1.3g of N-methylpyrrolidoneDissolving the agent; at the same time, 0.0125g (2.5%) of the pore-forming agent polyethylene glycol was dissolved in 0.04g of N-methylpyrrolidone solvent. And mixing the dissolved electrode active substance, the conductive agent, the binder and the dissolved pore-forming agent polyethylene glycol, and stirring for 5 hours on a stirrer to form uniformly mixed thick slurry in a black state. And uniformly coating the slurry on the aluminum foil by adopting coating equipment to obtain the electrode-current collector integrated electrode. The thickness of the coated electrode was 1000. mu.m. And (3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 100 ℃ for drying for 12 h. Punching the dried integrated electrode into a wafer electrode with the diameter of 14mm, taking the wafer electrode as a positive electrode, taking a metal sodium sheet as a negative electrode, and taking 1M NaClO as a negative electrode4(the volume ratio of Ethylene Carbonate (EC)/diethyl carbonate (DEC) is 1:1 and 2 wt.% FEC) is used as electrolyte, and a sodium ion battery is assembled. The active material loading of the assembled sodium-ion battery is about 15mg cm-2。
Example 4: (5% polyethylene glycol as pore-forming agent)
Electrode active material (positive electrode material is selected from sodium vanadium phosphate, 0.35 g), conductive agent (Super P, 0.1 g) and binder (PVDF, 0.05 g) are mixed according to the mass ratio of 70%: 20%: 10% were mixed and dissolved in 1.3g of N-methylpyrrolidone solvent; at the same time, 0.025g (5%) of a pore-forming agent, polyethylene glycol, was dissolved in 0.04g of N-methylpyrrolidone solvent. And mixing the dissolved electrode active substance, the conductive agent, the binder and the dissolved pore-forming agent polyethylene glycol, and stirring for 5 hours on a stirrer to form uniformly mixed thick slurry in a black state. And uniformly coating the slurry on the aluminum foil by adopting coating equipment to obtain the electrode-current collector integrated electrode. The thickness of the coated electrode was 1000. mu.m. And (3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 100 ℃ for drying for 12 h. Punching the dried integrated electrode into a wafer electrode with the diameter of 14mm, taking the wafer electrode as a positive electrode, taking a metal sodium sheet as a negative electrode, and taking 1M NaClO as a negative electrode4(the volume ratio of Ethylene Carbonate (EC)/diethyl carbonate (DEC) is 1:1 and 2 wt.% FEC) is used as electrolyte, and a sodium ion battery is assembled. The active material loading of the assembled sodium-ion battery is about 15mg cm-2。
Comparative example:
electrode active material (positive electrode material is selected from sodium vanadium phosphate, 0.35 g), conductive agent (Super P, 0.1 g) and binder (PVDF, 0.05 g) are mixed according to the mass ratio of 70%: 20%: 10 percent of the mixture is mixed and dissolved by 1.3g of N-methyl pyrrolidone solvent, and the mixture is stirred for 5 hours to prepare slurry which is uniformly mixed and is in a black sticky state. And uniformly coating the slurry on the aluminum foil by adopting coating equipment to obtain the electrode-current collector integrated electrode. The thickness of the coated electrode was 1000. mu.m. And (3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 100 ℃ for drying for 12 h. Punching the dried integrated electrode into a wafer electrode with the diameter of 14mm, taking the wafer electrode as a positive electrode, taking a metal sodium sheet as a negative electrode, and taking 1M NaClO as a negative electrode4(the volume ratio of Ethylene Carbonate (EC)/diethyl carbonate (DEC) is 1:1 and 2 wt.% FEC) is used as electrolyte, and a sodium ion battery is assembled. The active material loading of the assembled sodium-ion battery is about 15mg cm-2。
Effects of the implementation
With a suitable amount of NH4H2CO3And polyethylene glycol as a pore-forming agent, as shown in figure 1, has a fluffy porous structure, is favorable for promoting the diffusion and mass transfer of sodium ions in the electrode, and can obviously improve the rate capability of a battery assembled by the high-load electrode.
As can be seen from FIG. 2, 2.5% NH was added4H2CO3The high-supported electrode prepared as the pore-forming agent, namely the battery assembled in example 1, has better rate performance than the comparative example, as shown in fig. 2, the difference between the two is smaller under the low rates of 0.2C, 0.5C and 1C, and the difference between the two performances is more and more obvious after the rate is increased to 2C. At 2C rate, the capacity of example 1 was 108mAh g-1Compared with the comparative example, the improvement of 13mAh g-1(ii) a At 5C rate, the capacity of example 1 was 98mAh g-1Compared with the comparative example, the improvement is 22mAh g-1(ii) a At a high magnification of 8C, example 1 also retained 86mAh g-1The specific capacity is improved by 25mAh g compared with the comparative example-1；
As can be seen from FIG. 3, addition5% NH4H2CO3The high-supported electrode prepared as the pore-forming agent, namely the battery assembled in example 2, also has better rate performance than the comparative example, as shown in fig. 3, the difference between the two is smaller under the low rates of 0.2C, 0.5C and 1C, and the difference between the two performances is more and more obvious after the rate is increased to 2C. At 2C rate, the capacity of example 2 was 108mAh g-1Compared with the comparative example, the improvement of 13mAh g-1(ii) a At 5C rate, the capacity of example 2 was 99mAh g-1Compared with the comparative example, the improvement is 23mAh g-1(ii) a At high rates of 8C, example 2 had up to 90mAh g-1The specific capacity is improved by about 30mAh g compared with the comparative example-1Specific capacity of (a);
as can be seen from fig. 4, the high-supported electrode prepared by adding 2.5% of polyethylene glycol as a pore-forming agent, i.e., the battery assembled in example 3, also has better rate performance than the comparative example, as shown in fig. 4, the difference between the two is smaller at low rates of 0.2C, 0.5C and 1C, and the difference between the two performances is more and more obvious after the rate is increased to 2C. At 2C rate, the capacity of example 3 was 108mAh g-1Compared with the comparative example, the improvement of 13mAh g-1(ii) a At 5C rate, the capacity of example 3 was 98mAh g-1Compared with the comparative example, the improvement is 22mAh g-1(ii) a At high rates of 8C, example 3 had up to 88mAh g-1The specific capacity is improved by 27mAh g compared with the comparative example-1Specific capacity of (a);
as can be seen from fig. 5, the high-supported electrode prepared by adding 5% of polyethylene glycol as a pore-forming agent, i.e., the battery assembled in example 4, also has better rate performance than the comparative example, as shown in fig. 5, the difference between the two is smaller at low rates of 0.2C, 0.5C and 1C, and the difference between the two performances is more and more obvious after the rate is increased to 2C. At 2C rate, the capacity of example 4 was 107mAh g-1Compared with the comparative example, the improvement of 12mAh g-1(ii) a At 5C rate, the capacity of example 4 was 102mAh g-1Compared with the comparative example, the improvement of 26mAh g-1(ii) a At high rates of 8C, example 4 had up to 89mAh g-1The specific capacity is improved by 28mAh g compared with the comparative example-1The specific capacity of (A).

Claims (6)

1. The application of the high-load active material electrode in the sodium ion battery is characterized in that the electrode adopts the following preparation method:
1) mixing an electrode active substance, a conductive agent and a binder into a solute, and dissolving the solute by using an N-methylpyrrolidone solvent, wherein the solute accounts for 20-50% of the mass of the solution; meanwhile, dissolving a pore-forming agent in an N-methyl pyrrolidone solvent, wherein the pore-forming agent accounts for 20-50% of the total mass of the solvent and the pore-forming agent; the mixing mass ratio of the electrode active substance, the conductive agent and the binder is (50-90): 5-20): 5-30); mixing the dissolved electrode active substance, the conductive agent, the binder and the dissolved pore-forming agent, and stirring for 4-6h to form slurry;
2) coating the slurry on an aluminum foil to obtain an electrode-current collector integrated electrode;
3) putting the prepared electrode-current collector integrated electrode into a constant-temperature oven at 100 ℃ for drying for 12-24 h;
wherein the pore-forming agent is one or more than two of 2, 4, 6-trinitrotoluene, carbon powder, polyvinyl alcohol (PVA), polyethylene glycol (PEG), starch, PMMA, ammonium bicarbonate, urea and polyvidone (PVP);
the pore-forming agent accounts for 2.5-10% of the total mass of the electrode active substance, the conductive agent and the binder; the electrode active material content is 15-30mg/cm2。
2. Use according to claim 1, characterized in that: the electrode active material in the step 1) is used as a positive electrode material or a negative electrode material, and the positive electrode material is one or more than two of an oxide, a polyanion compound and a Prussian blue compound; the negative electrode material is one or more than two of carbon-based material, alloy material and phosphate.
3. Use according to claim 1, characterized in that: the conductive agent in the step 1) is one or more than two of Super P, carbon black, reduced graphene oxide, Ketjen black and acetylene black carbon materials; the binder is one or more than two of PVDF, PVDF-HFP and PTFE.
4. Use according to claim 1, characterized in that: the supporting amount of the electrode active material is controlled by the thickness of the electrode coated on the aluminum foil; the thickness of the coated electrode was 400-2000 um.
5. Use according to claim 2, characterized in that: the oxide is NaCoO2、NaMnO2、NaFeO2、NaxFe0.5Mn0.5O2、NaNi0.5Mn0.5O2、Na2/3Ni1/3Mn2/3O2、NaNi1/3Mn1/3Co1/3O2、NaNi1/3Fe1/3Mn1/3O2、Na0.44MnO2One or more than two of them; the polyanionic compound is NaFePO4、Na2FeP2O7、Na4Fe3(PO4)2P2O7、Na3V2(PO4)3、Na3NiZr（PO4)3、Na3V2(PO4)2F3、Na2FePO4F、Na2FeSiO4One or more than two of them; the Prussian blue compound is Na4Fe(CN)6、Na1.72MnFe(CN)6One or more than two of them.
6. Use according to claim 2, characterized in that: the carbon-based material is one or more than two of graphene, hard carbon and soft carbon; the alloy material is one or more of Sb/C, SnSb/C and Sn/C; the phosphate is Na3V2(PO4)3、 NaTi2(PO4)3And Na3MnTi（PO4）3One or more than two of them.
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