CN114604905B - Preparation method of ternary battery anode material combining plasmas with sulfate - Google Patents

Preparation method of ternary battery anode material combining plasmas with sulfate Download PDF

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CN114604905B
CN114604905B CN202210151531.5A CN202210151531A CN114604905B CN 114604905 B CN114604905 B CN 114604905B CN 202210151531 A CN202210151531 A CN 202210151531A CN 114604905 B CN114604905 B CN 114604905B
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nitrogen
nickel cobalt
lithium manganate
cobalt lithium
carbazolyl
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张怡
徐杰
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Shanghai Liming Technology Co ltd
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Abstract

The invention relates to the technical field of battery anode materials, and discloses a ternary battery anode material of plasma combined sulfate, which comprises alkynyl and carbazolyl diacetylene benzene of a carbazole structural unit, wherein a coating layer of carbazolyl cross-linked polymer is generated on the surface of nickel cobalt lithium manganate through dimethoxy methane cross-linking, the carbazolyl cross-linked polymer contains carbazole nitrogen heterocycle, rigid aromatic ring and alkynyl, the carbon content is high, a nitrogen-doped carbon layer with stable structure is obtained through high-temperature carbonization, the nitrogen content on the surface of the carbon layer is further improved through ammonia plasma surface modification, the nitrogen-doped carbon layer has rich nitrogen-containing functional groups such as graphite nitrogen, pyrrole nitrogen and the like, the conductivity and the electrochemical performance of the carbon coating layer are improved, and the oxygen-containing functional groups are generated on the surface of the nitrogen-doped carbon layer through ammonium persulfate oxidation, so that the wettability of the nickel cobalt lithium manganate coated by the nitrogen-doped carbon layer in electrolyte is improved, and the surface mass transfer process is promoted.

Description

Preparation method of ternary battery anode material combining plasmas with sulfate
Technical Field
The invention relates to the technical field of battery anode materials, in particular to a ternary battery anode material of plasma combined sulfate.
Background
The lithium battery is mainly made of a positive electrode, a negative electrode, electrolyte, a diaphragm and the like, wherein the positive electrode material has great influence on the electrochemical performance of the lithium battery, the current positive electrode material of the lithium battery is mainly made of lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide and the like, the nickel cobalt lithium manganate has high specific capacity, good safety and environmental protection without pollution, and the lithium battery has wide application in ternary positive electrode materials of the lithium battery, such as a patent of nitrogen-doped carbon-coated ternary positive electrode material and a preparation method thereof, and the electrochemical performance of the nitrogen-doped carbon-coated ternary positive electrode material obtained by calcining the ternary positive electrode material coated by citric acid and polyvinylpyrrolidone is excellent; the invention aims to synthesize a novel carbazolyl cross-linked polymer coated nickel cobalt lithium manganate and a novel carbazolyl cross-linked polymer coated nickel cobalt lithium manganate which are high in specific capacity and superior in cycle performance.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a ternary battery anode material of plasma combined sulfate.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the ternary battery anode material combining the plasmas with the sulfate comprises the following steps:
(1) Dissolving 3-bromo-9-phenyl-9H-carbazole and p-diacetylene benzene into toluene and triethylamine, tetra (triphenylphosphine) palladium and cuprous iodide, performing heating reflux reaction, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2).
(2) Dissolving carbazolyl diacetylene benzene into 1, 2-dichloroethane, adding nickel cobalt lithium manganate, performing ultrasonic dispersion, adding ferric trichloride and dimethoxymethane, heating to 70-90 ℃ for reaction of 15-30 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 700-800 ℃ in a nitrogen atmosphere, and carbonizing 2-4 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 3-10 min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate at the ammonia flow rate of 10-30 mL/min.
(5) And placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution, stirring at 30-50 ℃ for activation of 2-4 h, filtering, and washing with deionized water to obtain the ternary battery anode material modified by plasma combined sulfate.
Preferably, the weight ratio of 3-bromo-9-phenyl-9H-carbazole, p-diacetylene benzene, tetrakis (triphenylphosphine) palladium and cuprous iodide in step (1) is 480-560:100:40-65:12-22.
Preferably, the reaction in step (1) is stirred at 65-80 ℃ and refluxed for 12-36 h.
Preferably, the weight ratio of the carbazolyl diacetylene benzene, the nickel cobalt lithium manganate, the ferric trichloride and the dimethoxy methane in the step (2) is 100:600-1400:80-140:45-60.
Preferably, the concentration of the ammonium persulfate aqueous solution in the step (5) is 18-30%.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the ternary battery anode material combining the sulfate with the plasma, 3-bromo-9-phenyl-9H-carbazole and p-diacetylene benzene are utilized to synthesize the novel p-carbazolyldiacetylene benzene containing alkynyl and carbazole structural units through a Sonogashira coupling reaction, nickel cobalt lithium manganate is used as a carrier, dimethoxymethane is used for crosslinking, a coating layer of carbazolyl crosslinked polymer is generated on the surface of the nickel cobalt lithium manganate, the carbazolyl crosslinked polymer contains carbazole nitrogen heterocycle, rigid aromatic ring and alkynyl, the carbon content is high, a nitrogen-doped carbon layer with stable structure is obtained through high-temperature carbonization, the nitrogen content on the surface of the carbon layer is further improved through ammonia plasma surface modification, the nitrogen-doped carbon layer has rich nitrogen-containing functional groups such as graphite nitrogen, pyrrole nitrogen and the like, the conductivity and electrochemical performance of the carbon coating layer are improved, and further through ammonium persulfate oxidation, the oxygen-containing functional groups are generated on the surface of the nitrogen-doped carbon layer, the wettability of the nickel cobalt lithium manganate coated on electrolyte is favorably improved, the surface mass transfer process is promoted, and the ternary battery anode material combining the sulfate shows excellent practical specific capacity and cycle stability.
Description of the embodiments
To achieve the above object, the present invention provides the following embodiments and examples: the preparation method of the ternary battery anode material combining the plasmas with the sulfate comprises the following steps:
(1) Dissolving 3-bromo-9-phenyl-9H-carbazole and p-diacetylene benzene into toluene and triethylamine, tetra (triphenylphosphine) palladium and cuprous iodide, wherein the weight ratio of 3-bromo-9-phenyl-9H-carbazole, p-diacetylene benzene, tetra (triphenylphosphine) palladium and cuprous iodide is 480-560:100:40-65:12-22, heating to 65-80 ℃, stirring and refluxing to react 12-36H, cooling and decompressing, distilling after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2), wherein the reaction formula is:
(2) Dissolving carbazolyl diacetylene benzene into 1, 2-dichloroethane, adding nickel cobalt lithium manganate (LiNi0.6Co0.2Mn0.2O2), performing ultrasonic dispersion, adding ferric trichloride and dimethoxymethane, wherein the weight ratio of the carbazolyl diacetylene benzene, the nickel cobalt lithium manganate, the ferric trichloride and the dimethoxymethane is 100:600-1400:80-140:45-60, heating to 70-90 ℃, reacting for 15-30 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 700-800 ℃ in a nitrogen atmosphere, and carbonizing 2-4 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 3-10 min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate at the ammonia flow rate of 10-30 mL/min.
(5) And (3) placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution with the concentration of 18-30%, stirring at the temperature of 30-50 ℃ for activation of 2-4 h, filtering, and washing with deionized water to obtain the plasma combined sulfate modified ternary battery anode material.
Examples
(1) Dissolving 2.4 g of 3-bromo-9-phenyl-9H-carbazole and 0.5 g of p-diacetylene benzene into 15 mL of toluene and 5 mL of triethylamine, 0.2 g of tetra (triphenylphosphine) palladium and 0.06 g of cuprous iodide, heating to 80 ℃, stirring and refluxing to react 12H, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2)
(2) Dissolving 1 g p-carbazolyl diacetylene benzene into 100 mL of 1, 2-dichloroethane, adding 6 g of lithium nickel cobalt manganese oxide, performing ultrasonic dispersion, adding 0.8 g of ferric trichloride and 0.45 g of dimethoxymethane, heating to 80 ℃ to react 15 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl crosslinked polymer coated lithium nickel cobalt manganese oxide.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 800 ℃ under the nitrogen atmosphere, and carbonizing 2 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 10 min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate at the ammonia flow rate of 30 mL/min.
(5) And (3) placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution with the concentration of 20%, stirring at 40 ℃ for activation of 2 h, filtering, and washing with deionized water to obtain the ternary battery anode material modified by combining plasmas with sulfate.
Examples
(1) Dissolving 2.4 g of 3-bromo-9-phenyl-9H-carbazole and 0.5 g of p-diacetylene benzene into 15 mL of toluene and 5 mL of triethylamine, 0.25 g of tetra (triphenylphosphine) palladium and 0.07 g of cuprous iodide, heating to 80 ℃, stirring and refluxing to react for 24H, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2)
(2) Dissolving 1 g p-carbazolyl diacetylene benzene into 150 mL of 1, 2-dichloroethane, adding 8 g of lithium nickel cobalt manganese oxide, performing ultrasonic dispersion, adding 1 g of ferric trichloride and 0.5 g of dimethoxymethane, heating to 70 ℃ to react for 30 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl cross-linked polymer coated lithium nickel cobalt manganese oxide.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 750 ℃ in a nitrogen atmosphere, and carbonizing 3 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 5 min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate at the ammonia flow rate of 10 mL/min.
(5) And (3) placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution with the concentration of 20%, stirring at 40 ℃ for activation of 3 h, filtering, and washing with deionized water to obtain the ternary battery anode material modified by combining plasmas with sulfate.
Examples
(1) Dissolving 2.7 g of 3-bromo-9-phenyl-9H-carbazole and 0.5 g of p-diacetylene benzene into 20 mL of toluene and 10 mL of triethylamine, 0.28 g of tetra (triphenylphosphine) palladium and 0.09 g of cuprous iodide, heating to 80 ℃, stirring and refluxing to react 24H, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2)
(2) Dissolving 1 g p-carbazolyl diacetylene benzene into 150 mL of 1, 2-dichloroethane, adding 12 g of lithium nickel cobalt manganese oxide, performing ultrasonic dispersion, adding 1.2 g of ferric trichloride and 0.55 g of dimethoxymethane, heating to 90 ℃ to react 15 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl crosslinked polymer coated lithium nickel cobalt manganese oxide.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 750 ℃ in a nitrogen atmosphere, and carbonizing 3 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 8 min, wherein the flow rate of ammonia is 10 mL/min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate.
(5) And (3) placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution with the concentration of 25%, stirring at 30 ℃ for activation of 4 h, filtering, and washing with deionized water to obtain the ternary battery anode material modified by combining plasmas with sulfate.
Examples
(1) Dissolving 2.8 g of 3-bromo-9-phenyl-9H-carbazole and 0.5 g of p-diacetylene benzene into 30 mL of toluene and 12 mL of triethylamine, 0.32 g of tetrakis (triphenylphosphine) palladium and 0.11 g of cuprous iodide, heating to 70 ℃, stirring and refluxing to react 12H, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2)
(2) Dissolving 1 g p-carbazolyl diacetylene benzene into 200 mL of 1, 2-dichloroethane, adding 14 g of lithium nickel cobalt manganese oxide, performing ultrasonic dispersion, adding 1.4 g of ferric trichloride and 0.6 g of dimethoxymethane, heating to 70 ℃ to react for 30 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl crosslinked polymer coated lithium nickel cobalt manganese oxide.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 700 ℃ under the nitrogen atmosphere, and carbonizing 4 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 5 min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate at the ammonia flow rate of 15 mL/min.
(5) And (3) placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution with the concentration of 30%, stirring at the temperature of 30 ℃ for activation of 4 h, filtering, and washing with deionized water to obtain the ternary battery anode material modified by combining plasmas with sulfate.
Comparative example 1
(1) Dissolving 2.5 g of 3-bromo-9-phenyl-9H-carbazole and 0.5 g of p-diacetylene benzene into 20 mL of toluene and 8 mL of triethylamine, 0.25 g of tetra (triphenylphosphine) palladium and 0.06 g of cuprous iodide, heating to 70 ℃, stirring and refluxing to react 36H, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2)
(2) Dissolving 1 g p-carbazolyl diacetylene benzene into 150 mL of 1, 2-dichloroethane, adding 8 g of lithium nickel cobalt manganese oxide, performing ultrasonic dispersion, adding 1 g of ferric trichloride and 0.5 g of dimethoxymethane, heating to 80 ℃ to react for 20 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl cross-linked polymer coated lithium nickel cobalt manganese oxide.
(3) And (3) placing the carbazolyl cross-linked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 800 ℃ under the nitrogen atmosphere, and carbonizing 3 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate serving as the ternary battery anode material.
Comparative example 2
(1) Dissolving 2.6 g of 3-bromo-9-phenyl-9H-carbazole and 0.5 g of p-diacetylene benzene into 30 mL of toluene and 12 mL of triethylamine, 0.32 g of tetrakis (triphenylphosphine) palladium and 0.1 g of cuprous iodide, heating to 80 ℃, stirring and refluxing to react 24H, cooling and distilling under reduced pressure after the reaction, washing with diethyl ether and deionized water, adding ethyl acetate, and recrystallizing to obtain p-carbazolyldiacetylene benzene (C46H 28N 2)
(2) Dissolving 1 g p-carbazolyl diacetylene benzene into 200 mL of 1, 2-dichloroethane, adding 12 g of lithium nickel cobalt manganese oxide, performing ultrasonic dispersion, adding 1.4 g of ferric trichloride and 0.6 g of dimethoxymethane, heating to 80 ℃ to react for 30 h, cooling after the reaction, performing reduced pressure distillation, and washing sequentially by dichloromethane, acetone, deionized water and methanol to obtain the carbazolyl crosslinked polymer coated lithium nickel cobalt manganese oxide.
(3) And (3) placing the carbazolyl crosslinked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 750 ℃ in a nitrogen atmosphere, and carbonizing 4 h to obtain the nitrogen-doped carbon coated nickel cobalt lithium manganate.
(4) And (3) putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 3 min, wherein the flow rate of ammonia is 20 mL/min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate serving as a ternary battery anode material.
Adding a ternary battery anode material, conductive carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1 into N-methyl pyrrolidone, uniformly mixing, coating the slurry on the surface of an aluminum foil, drying to prepare an anode plate, using the lithium plate as a cathode, using an LiPF6 solution as an electrolyte and using a polypropylene porous diaphragm to assemble a button CR2032 battery, and testing the electrochemical performance by using a CHI760D electrochemical workstation.
Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2
Multiplying power (C) 0.5 0.5 0.5 0.5 0.5 0.5
Specific capacity for initial discharge (mAh/g) 166.9 150.8 139.1 131.4 126.7 132.0
Specific discharge capacity (mAh/g) of 50 circles of circulation 144.3 136.8 130.1 120.6 105.4 106.8
Capacity retention (%) 86.5 90.7 93.5 91.8 83.2 80.9
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims (5)

1. A preparation method of a ternary battery anode material combining plasmas with sulfate is characterized by comprising the following steps: the preparation method of the positive electrode material comprises the following steps:
(1) Dissolving 3-bromo-9-phenyl-9H-carbazole and p-diacetylene benzene into toluene and triethylamine, tetra (triphenylphosphine) palladium and cuprous iodide, and performing heating reflux reaction to obtain p-carbazolyl diacetylene benzene (C) 46 H 28 N 2 ）；
(2) Dissolving p-carbazolyl diacetylene benzene into 1, 2-dichloroethane, adding nickel cobalt lithium manganate, performing ultrasonic dispersion, adding ferric trichloride and dimethoxymethane, heating to 70-90 ℃ for reaction 15-30 h, and obtaining carbazolyl crosslinked polymer coated nickel cobalt lithium manganate;
(3) Placing carbazolyl cross-linked polymer coated nickel cobalt lithium manganate in an atmosphere tube furnace, heating to 700-800 ℃ under nitrogen atmosphere, and carbonizing 2-4 h to obtain nitrogen-doped carbon coated nickel cobalt lithium manganate;
(4) Putting the nitrogen-doped carbon-coated nickel cobalt lithium manganate into a dielectric barrier plasma reaction device, performing ammonia dielectric barrier discharge plasma modification for 3-10 min, and preparing the ammonia plasma modified nitrogen-doped carbon-coated nickel cobalt lithium manganate at the ammonia flow rate of 10-30 mL/min;
(5) And placing the ammonia gas plasma modified nitrogen-doped carbon layer coated nickel cobalt lithium manganate in an ammonium persulfate aqueous solution, stirring at 30-50 ℃ for activation of 2-4 h, filtering, and washing with deionized water to obtain the ternary battery anode material modified by plasma combined sulfate.
2. The method for preparing the ternary battery anode material by combining plasmas with sulfate, which is characterized in that: in the step (1), the weight ratio of 3-bromo-9-phenyl-9H-carbazole, p-diacetylene benzene, tetrakis (triphenylphosphine) palladium and cuprous iodide is 480-560:100:40-65:12-22.
3. The method for preparing the ternary battery anode material by combining plasmas with sulfate, which is characterized in that: the reaction in the step (1) is stirred and refluxed at 65-80 ℃ for 12-36 h.
4. The method for preparing the ternary battery anode material by combining plasmas with sulfate, which is characterized in that: in the step (2), the weight ratio of the carbazolyl diacetylene benzene, the nickel cobalt lithium manganate, the ferric trichloride and the dimethoxy methane is 100:600-1400:80-140:45-60.
5. The method for preparing the ternary battery anode material by combining plasmas with sulfate, which is characterized in that: the concentration of the ammonium persulfate aqueous solution in the step (5) is 18-30%.
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