CN102082284B - Method for preparing anode supporting type intermediate-temperate solid oxide fuel cell (SOFC) - Google Patents

Method for preparing anode supporting type intermediate-temperate solid oxide fuel cell (SOFC) Download PDF

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CN102082284B
CN102082284B CN201010618297XA CN201010618297A CN102082284B CN 102082284 B CN102082284 B CN 102082284B CN 201010618297X A CN201010618297X A CN 201010618297XA CN 201010618297 A CN201010618297 A CN 201010618297A CN 102082284 B CN102082284 B CN 102082284B
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屠恒勇
余晴春
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Shanghai Jiaotong University
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Abstract

The invention relates to a method for preparing an anode supporting type intermediate-temperate solid oxide fuel cell (SOFC) in the technical field of fuel cells. The method comprises the following steps of: preparing an anode supporting body green stock by adopting a cast method; respectively depositing an anode functional layer and an electrolyte layer on the anode supporting body green stock by adopting a silk screen printing method; co-firing at certain temperature to obtain a half cell; depositing a barrier layer on the surface of the electrolyte by adopting the silk screen printing method and firing at certain temperature; and finally, depositing a cathode layer on the surface of the barrier layer by adopting the silk screen printing method, and firing at certain temperature to obtain a single cell. The invention has the advantages that the cast method and the silk screen printing method are combined to prepare the anode supporting SOFC single cell to form a simple, low-cost and scaled preparation process, and single cells in various different sizes can be prepared, thus the method has a favorable industrialization prospect.

Description

The preparation method of anode support type intermediate temperature solid oxide fuel cell
Technical field
What the present invention relates to is the method in a kind of fuel cell technology field, specifically is a kind of preparation method of anode support type intermediate temperature solid oxide fuel cell.
Background technology
SOFC (Solid Oxide Fuel Cell; SOFC) be a kind of all solid state power generating device that the chemical energy in the fuel directly is transformed into electric energy through electrochemical reaction; It does not need the transition process through the fuel chemical energy → heat energy of associating → mechanical energy → electric energy; Have many advantages, for example: (1) does not need to make electrode with noble metal; (2) broad applicability of fuel, promptly hydrogen, carbon monoxide and hydrocarbon all can be used as fuel; (3) has higher ability transformation efficiency; (4) quick electrode reaction; (5) only be the gas-solid binary system, eliminated the etching problem that liquid electrolyte produced; (6) the high-quality waste gas that gives off can with gas turbine combined cycle, or cogeneration.SOFC has application fields, and it is mainly used and comprises distributed power station, family power station, vehicle accessory power supply, uninterrupted power supply and military power supply etc.
The developmental research of SOFC and commercialization have received the generally attention of many countries in the world, generally have an optimistic view of the application prospect of SOFC in the world.At present, the major obstacle of SOFC entering commercialized development is battery system life-span and price.Flat solid oxide fuel cell; Especially intermediate temperature solid oxide fuel cell (500～800 ℃) is the forward position and the focus of the present research of SOFC in the world, and its most outstanding advantage is when guaranteeing high power density; Can use cheap alloys such as stainless steel as metallic interconnect materials; Reduce the requirement that sealing is waited other material, can adopt ceramic cheaply preparation technology, be expected significantly to reduce the manufacturing cost of SOFC.Wherein, (YSZ: yttrium stable zirconium oxide) the anode-supported intermediate temperature solid oxide fuel cell has obtained paying attention to widely Ni-YSZ in recent years in the world, and the preparation technology of monocell comprises The tape casting, slip casting, plasma spraying, wet spray, silk screen printing, vapour deposition, spray pyrolysis, sol-gel method, electrophoretic deposition and high temperature sintering etc.
Literature search through to prior art is found; Chinese patent notification number CN1933229A; Name is called the patent of " preparation of solid oxide fuel cell of anode-supported ", has introduced employing gel injection-moulding prepared porous anode matrix, the fine and close solid electrolyte film of spin coating process preparation; The double-deck green compact of anode and electrolyte are carried out high temperature co-firing, and utilization slurry coating processes prepares the negative electrode of battery and sintering at high temperature.
In addition; Chinese patent notification number CN101399352A, name is called the patent of " a kind of preparation method of high strength ultra-thin anode supporting type solid oxide fuel cell ", has introduced the employing The tape casting and has prepared the anode support green compact; Use the direct spraying process of air that active anode slurry and electrolyte slurry are sprayed on the anode support green compact; Obtain half-cell through high-temperature roasting, through air spray finishing cathode slurry is sprayed on the half-cell at last, make monocell through high-temperature roasting.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method of anode support type intermediate temperature solid oxide fuel cell is provided; Adopt The tape casting to prepare the anode support green compact; Adopt silk screen print method difference deposition anode functional layer and dielectric substrate on the anode support green compact, co-sintering obtains half-cell at a certain temperature, adopts silk screen print method also to carry out sintering at a certain temperature at the bath surface deposited barrier layer again; Adopt silk screen print method at barrier layer surface deposition cathode layer at last, sintering makes monocell at a certain temperature.The invention has the advantages that combines The tape casting and silk screen print method carries out the preparation of anode-supported SOFC monocell, but forms the preparation technology of simple, low-cost and scale, can make the monocell of various different sizes, has good industrialization prospect.
The present invention realizes through following technical scheme, the present invention includes following steps:
The first step, yttria-stabilized zirconia (YSZ) and nickel oxide (NiO) were prepared burden by weight 60: 40～30: 70; 20～the 30wt% that presses YSZ and NiO compound adds the starch pore former; Add mixed solvent and triethyl phosphate dispersant successively, and carry out the ball milling first time with planetary ball mill.
Described mixed solvent is meant that butanone and ethanol were by 2: 1 weight ratio proportionings.
The concentration of described triethyl phosphate dispersant is 1～5wt%.
Described first time, ball milling was meant: with 6～10 hours mixings of 100～400rpm rotating speed ball milling.
Second step, in the slurry of ball milling for the first time, add polyvinyl butyral resin binding agent, dibutyl phthalate and Macrogol 200 plastic agent successively, and carrying out the ball milling second time.
The concentration of described polyvinyl butyral resin binding agent is 10～20wt%.
The concentration of described dibutyl phthalate is 4～10wt%.
The concentration of described Macrogol 200 plastic agent is 4～10wt%.
Described second time, ball milling was meant: with planetary ball mill with 100～400rpm rotating speed, 14～18 hours mixings of ball milling again.
The 3rd the step, will through the second time ball milling slurry process the anode support green compact; Concrete steps comprise: at first vacuum degassing is handled; On casting machine, regulate the scraper height and carry out curtain coating and process the anode support green compact, dried anode support green compact are cut to required size by desired thickness.
The 4th goes on foot, ethyl cellulose is dissolved in processes terpineol solution of ethyl cellulose in the terpinol, and uses binding agent as silk screen printing.
The ethyl cellulose cellulose content is 1～5wt% in the described terpineol solution of ethyl cellulose.
The 5th the step, with scandium oxide and ceria stabilized Zirconium powder; Being 10Sc1CeSZ and NiO mixed powder joins in the terpineol solution of ethyl cellulose by 60: 40～30: 70 weight ratio; After grinding, obtain anode slurry, form anode functional layer on the screen process press anode slurry for preparing being deposited on the anode support green compact equably;
The weight ratio of described 10Sc1CeSZ and NiO mixed powder and terpineol solution of ethyl cellulose is 1.5～4.0;
Described anode functional layer THICKNESS CONTROL is at 5-10 μ m.
The 6th goes on foot, scandium oxide and ceria stabilized Zirconium powder is joined in the terpineol solution of ethyl cellulose; After grinding, obtain electrolyte slurry, on the screen process press electrolyte slurry for preparing is being deposited on formation dielectric substrate on the anode functional layer equably.
The weight ratio of described scandium oxide and ceria stabilized Zirconium powder and terpineol solution of ethyl cellulose is 1.5～4.0;
The 7th step, anode support green compact, anode functional layer and dielectric substrate that above-mentioned the 3rd step, the 5th step and the 6th step are prepared pass through the plastic removal sintering processes respectively, obtain the anode-supported half-cell.
Described plastic removal sintering processes is meant: with plastic removal under 600 ℃ of environment 2～4 hours, with 1400～1500 ℃ of sintering 2～6 hours, wherein the intensification of plastic removal and sintering and rate of temperature fall were 0.5～5 ℃/min then in air.
The 8th goes on foot, the doped cerium oxide powder is added in the terpineol solution of ethyl cellulose; Obtain the doped cerium oxide slurry through grinding; Form the barrier layer on the screen process press doped cerium oxide slurry for preparing being deposited on the bath surface equably, behind the sintering of barrier layer, obtain combining good barrier layer then with dielectric substrate.
The weight ratio of described doped cerium oxide powder and terpineol solution of ethyl cellulose is 1.5～4.0;
Described doped cerium oxide is samarium doped cerium oxide (Ce 1-xSm xO 2) or gadolinium doped cerium oxide (Ce 1-xGd xO 2).
Described barrier layer sintering is meant: 1200～1300 ℃ of sintering are 1～2 hour in air, and the intensification of sintering and rate of temperature fall are 1～5 ℃/min.
The 9th goes on foot, cathode powder is joined in the terpineol solution of ethyl cellulose; Obtain cathode slurry through grinding; Form cathode layer on the screen process press cathode slurry for preparing being deposited on the barrier layer surface equably; Combine good cathode layer with the barrier layer through the acquisition of cathode layer sintering then, thereby accomplish the preparation of monocell.
The weight ratio of described cathode powder and terpineol solution of ethyl cellulose is 1.5～4.0;
Described cathode powder is Rare-Earth Cobalt acid strontium oxide (Ln 1-xSr xCoO 3, Ln=La, Nd, Pr, Sm, Gd) or rare earth iron cobalt acid strontium oxide (Ln 1-xSr xFe 1-yCo yO 3, Ln=La, Nd, Pr, Sm, powder Gd), wherein 0≤x≤1,0≤y≤1.
Described cathode layer sintering is meant: 900～1200 ℃ of sintering are 2～4 hours in air, and control heats up and rate of temperature fall is 1～5 ℃/min.
The invention has the advantages that: with The tape casting and the silk screen print method preparation anode supporting type solid oxide individual fuel cell that combines; Can control the thickness and the uniformity of anode support and each thin layer easily; The electrolytic thin-membrane that obtains is very fine and close; And the porosity of controlling anode and negative electrode easily, realize high catalytic performance.Method technology of the present invention is simple, is convenient to amplify and the scale manufacturing.
Description of drawings
Fig. 1 is the micro-structure diagram by the electrolyte 10Sc1CeSZ surface of embodiment 1 preparation.
Fig. 2 is the micro-structure diagram by the half-cell section of embodiment 1 preparation.
Fig. 3 is the micro-structure diagram by the monocell section of embodiment 1 preparation.
Fig. 4 is the monocell performance by embodiment 1 preparation.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
(1) 32 gram yttria-stabilized zirconias (YSZ), 48 gram nickel oxide (NiO) and 20 gram starch are added in the ball grinder; The 90 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 8 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 12 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 16 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process the anode support green compact, dried anode support green compact thickness is 700 μ m.
(2) ethyl cellulose is dissolved in the terpinol, processes the terpineol solution of ethyl cellulose that the ethyl cellulose cellulose content is 2wt%, to be applied to the deposition of anode functional layer, dielectric substrate, barrier layer and cathode layer with binding agent as silk screen printing.The mixed powder that to make 1.5 gram scandium oxides and ceria stabilized zirconia (10Sc1CeSZ) and 1 gram NiO by oneself joins in 8 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h, form anode functional layer on the screen process press anode slurry for preparing being deposited on the anode support green compact equably.To make 4.5 gram 10Sc1CeSZ powders by oneself joins in 9 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h, on the screen process press electrolyte slurry for preparing is being deposited on formation dielectric substrate on the anode functional layer equably.
(3) with above-mentioned anode support green compact, anode functional layer and dielectric substrate 600 ℃ of plastic removals 2 hours in air, 1450 ℃ of sintering 4 hours, control heated up and rate of temperature fall is 2 ℃/min, is prepared into the anode-supported half-cell then.
(4) with 2 gram self-control gadolinium doped cerium oxide (Ce 0.8Gd 0.2O 2) powder joins in 3 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h; On the screen process press gadolinium doped cerium oxide slurry for preparing is being deposited on the bath surface and formation barrier layer equably; 1300 ℃ of sintering 1 hour in air then, control heats up and rate of temperature fall is 3 ℃/min, and acquisition combines good barrier layer with electrolyte.With 2.5 gram La 0.6Sr 0.4CoO 3Cathode powder joins in 5 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h; Form cathode layer on the screen process press cathode slurry for preparing being deposited on the barrier layer surface equably, 950 ℃ of sintering 2 hours in air then, control heats up and rate of temperature fall is 3 ℃/min; Acquisition combines good cathode layer with the barrier layer, thereby accomplishes the preparation of monocell.
As shown in Figure 1, prepared 10Sc1CeSZ dielectric substrate surface is very fine and close, and intergranule combines fine, though some hole of surface, these holes do not run through electrolytic thin-membrane.
As shown in Figure 2, prepared 10Sc1CeSZ dielectric substrate section is very fine and close, and the thickness of electrolytic thin-membrane is about 15 μ m, though section shows a little holes, these holes all are disconnected.
As shown in Figure 3, each interlayer combines closely in the prepared monocell, and supporter, anode and negative electrode demonstrate uniform pore structure.
As shown in Figure 4, prepared monocell is at 800 ℃, and the open circuit voltage of 700 ℃ and 600 ℃ is respectively 1.098V, and 1.115V and 1.133V are approaching with theoretical voltage, show that prepared 10Sc1CeSZ dielectric substrate is very fine and close; In current density is 1.25Acm -2The time, reach 911mW cm respectively in the power density of 800 ℃ and 700 ℃ -2With 729mW cm -2, and be 0.5A cm in current density -2The time, 600 ℃ power density is 161mW cm -2, show good performance.
Embodiment 2
(1) 36 gram yttria-stabilized zirconias (YSZ), 44 gram nickel oxide (NiO) and 20 gram starch are added in the ball grinder; The 90 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 10 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 12 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 14 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process the anode support green compact, dried anode support green compact thickness is 700 μ m.
(2) carry out terpineol solution of ethyl cellulose preparation, anode functional layer and dielectric substrate deposition by embodiment 1.
(3) carry out anode support green compact, anode functional layer and dielectric substrate co-sintering by embodiment 1, be prepared into the anode-supported half-cell.
(4) with 2 gram self-control samarium doped cerium oxide (Ce 0.8Sm 0.2O 2) powder joins in 3 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h; On the screen process press samarium doped cerium oxide slurry for preparing is being deposited on the bath surface and formation barrier layer equably; 1300 ℃ of sintering 1 hour in air then, control heats up and rate of temperature fall is 3 ℃/min, and acquisition combines good barrier layer with electrolyte.With 2.5 gram Sm 0.5Sr 0.5CoO 3Cathode powder joins in 5 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h; Form cathode layer on the screen process press cathode slurry for preparing being deposited on the barrier layer surface equably, 950 ℃ of sintering 2 hours in air then, control heats up and rate of temperature fall is 3 ℃/min; Acquisition combines good cathode layer with the barrier layer, thereby accomplishes the preparation of monocell.
Embodiment 3
(1) 40 gram yttria-stabilized zirconias (YSZ), 40 gram nickel oxide (NiO) and 20 gram starch are added in the ball grinder; The 90 gram butanone that add again by 2: 1 weight ratios restrain triethyl phosphates with alcohol mixed solvent and 2, with planetary ball mill with 8 hours mixings of 300rpm rotating speed ball milling.In the slurry of above-mentioned milling mixing, be equipped with 12 gram polyvinyl butyral resins respectively again, and 6 gram dibutyl phthalates and 6 gram Macrogol 200s, with planetary ball mill with 300rpm rotating speed 16 hours mixings of ball milling again.The slurry of above-mentioned last milling mixing is carried out vacuum degassing processing 30 minutes, on casting machine, carry out curtain coating and process the anode support green compact, dried anode support green compact thickness is 700 μ m.
(2) carry out terpineol solution of ethyl cellulose preparation, anode functional layer and dielectric substrate deposition by embodiment 1.
(3) carry out anode support green compact, anode functional layer and dielectric substrate co-sintering by embodiment 1, be prepared into the anode-supported half-cell.
(4) make the barrier layer by embodiment 1.With 2.5 gram La 0.6Sr 0.4Fe 0.8Co 0.2O 3Cathode powder joins in 5 milliliters of terpineol solution of ethyl cellulose; Grind the slurry that obtains stable uniform more than the 2h; Form cathode layer on the screen process press cathode slurry for preparing being deposited on the barrier layer surface equably, 950 ℃ of sintering 2 hours in air then, control heats up and rate of temperature fall is 3 ℃/min; Acquisition combines good cathode layer with the barrier layer, thereby accomplishes the preparation of monocell.

Claims (10)

1. the preparation method of an anode support type intermediate temperature solid oxide fuel cell is characterized in that, may further comprise the steps:
The first step, yttria-stabilized zirconia and nickel oxide are prepared burden by weight 60:40～30:70; 20～the 30wt% that presses YSZ and NiO compound adds the starch pore former; Add mixed solvent and triethyl phosphate dispersant successively, and carry out the ball milling first time with planetary ball mill;
Second step, in the slurry of ball milling for the first time, add polyvinyl butyral resin binding agent, dibutyl phthalate and Macrogol 200 plastic agent successively, and carrying out the ball milling second time;
The 3rd the step, will through the second time ball milling slurry process the anode support green compact; Concrete steps comprise: at first vacuum degassing is handled; On casting machine, regulate the scraper height and carry out curtain coating and process the anode support green compact, dried anode support green compact are cut to required size by desired thickness;
The 4th goes on foot, ethyl cellulose is dissolved in processes terpineol solution of ethyl cellulose in the terpinol, and uses binding agent as silk screen printing;
The 5th the step, with scandium oxide and ceria stabilized Zirconium powder; Being 10Sc1CeSZ and NiO mixed powder joins in the terpineol solution of ethyl cellulose by the weight ratio of 60:40～30:70; After grinding, obtain anode slurry, form anode functional layer on the screen process press anode slurry for preparing being deposited on the anode support green compact equably;
The 6th goes on foot, scandium oxide and ceria stabilized Zirconium powder is joined in the terpineol solution of ethyl cellulose; After grinding, obtain electrolyte slurry, on the screen process press electrolyte slurry for preparing is being deposited on formation dielectric substrate on the anode functional layer equably;
The 7th step, anode support green compact, anode functional layer and dielectric substrate that above-mentioned the 3rd step, the 5th step and the 6th step are prepared pass through the plastic removal sintering processes respectively, obtain the anode-supported half-cell;
The 8th goes on foot, the doped cerium oxide powder is added in the terpineol solution of ethyl cellulose; Obtain the doped cerium oxide slurry through grinding; Form the barrier layer on the screen process press doped cerium oxide slurry for preparing being deposited on the bath surface equably, behind the sintering of barrier layer, obtain combining good barrier layer then with dielectric substrate;
The 9th goes on foot, cathode powder is joined in the terpineol solution of ethyl cellulose; Obtain cathode slurry through grinding; Form cathode layer on the screen process press cathode slurry for preparing being deposited on the barrier layer surface equably; Combine good cathode layer with the barrier layer through the acquisition of cathode layer sintering then, thereby accomplish the preparation of monocell.
2. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that, the mixed solvent described in the first step is meant that butanone and ethanol are by 2:1 weight ratio proportioning; The concentration of described triethyl phosphate dispersant is 1～5wt%.
3. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1; It is characterized in that; In second step: the concentration of described polyvinyl butyral resin binding agent is 10～20wt%; The concentration of described dibutyl phthalate plasticizer is 4～10wt%, and the concentration of described Macrogol 200 plastic agent is 4～10wt%.
4. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that, the ethyl cellulose cellulose content is 1～5wt% in the described terpineol solution of ethyl cellulose.
5. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1; It is characterized in that the weight ratio of described 10Sc1CeSZ and NiO mixed powder, scandium oxide and ceria stabilized Zirconium powder, doped cerium oxide powder and cathode powder and terpineol solution of ethyl cellulose is 1.5～4.0.
6. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that, described plastic removal sintering processes is meant: in air with 600 oPlastic removal is 2～4 hours under the C environment, then with 1400～1500 oC sintering 2～6 hours, wherein the intensification of plastic removal and sintering and rate of temperature fall are 0.5～5 oC/min.
7. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that, described doped cerium oxide is samarium doped cerium oxide, i.e. Ce 1-xSm xO 2Or gadolinium doped cerium oxide, i.e. Ce 1-xGd xO 2
8. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that, described barrier layer sintering is meant: in air 1200～1300 oC sintering 1～2 hour, the intensification of sintering and rate of temperature fall are 1～5 oC/min.
9. according to the preparation method of claim 1 or 5 described anode support type intermediate temperature solid oxide fuel cells, it is characterized in that described cathode powder is Rare-Earth Cobalt acid strontium oxide, i.e. Ln 1-xSr xCoO 3, Ln=La, Nd, Pr, Sm, Gd or the acid of rare earth iron cobalt strontium oxide, i.e. Ln 1-xSr xFe 1-yCo yO 3, Ln=La, Nd, Pr, Sm, the powder of Gd, wherein 0<x<1,0<y<1.
10. the preparation method of anode support type intermediate temperature solid oxide fuel cell according to claim 1 is characterized in that, described cathode layer sintering is meant: in air 900～1200 oC sintering 2～4 hours, control heats up and rate of temperature fall is 1～5 oC/min.
CN201010618297XA 2010-12-30 2010-12-30 Method for preparing anode supporting type intermediate-temperate solid oxide fuel cell (SOFC) Expired - Fee Related CN102082284B (en)

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