CN1687773A - Method for accurate testing performance of pressure concentration-temperature of hydrogen storage material - Google Patents
Method for accurate testing performance of pressure concentration-temperature of hydrogen storage material Download PDFInfo
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- CN1687773A CN1687773A CN 200510046320 CN200510046320A CN1687773A CN 1687773 A CN1687773 A CN 1687773A CN 200510046320 CN200510046320 CN 200510046320 CN 200510046320 A CN200510046320 A CN 200510046320A CN 1687773 A CN1687773 A CN 1687773A
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- 238000000034 method Methods 0.000 title claims abstract description 85
- 238000012360 testing method Methods 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 title claims description 292
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 292
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 262
- 239000011232 storage material Substances 0.000 title claims description 94
- 230000008569 process Effects 0.000 claims abstract description 40
- 230000006835 compression Effects 0.000 claims abstract description 5
- 238000007906 compression Methods 0.000 claims abstract description 5
- 238000003860 storage Methods 0.000 claims description 82
- 150000002431 hydrogen Chemical class 0.000 claims description 35
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 238000003795 desorption Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 7
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 238000013507 mapping Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
This invention is a kind of method to measure the H2 storing material's PCT curved line. Especially it offers a kind of precise testing method which has wide use area to measure the H2 storing material's PCT curved line. This invention uses the volume method, that is to say, we will calculate the amount of H2 absorbed of the H2 storing material corresponding to different H2 pressure according to MBWR equation by continuously recording each part of pressure and temperature of H2 during the process of the H2 storing material absorbing or sending out H2, so as to get PCT curved line. After that we will realize the compression divisor's whole process of calculating and drawing picture by computer programming. As this invention has thought about the effect of the H2 storing room's temperature fluctuating, the PCT curved line will still be credible as though part of the room can not realize stable temperature. To sum up, this invention has good use value, making the instrument simple and easy to operate. At the same time we get higher degree of belief when we check the PCT curved line of carbon Nanometer pipe and V and so on which is the H2 storing material having high balance pressure.
Description
Technical field
The present invention provides the method for accurate testing of the PCT curve of the wide mensuration hydrogen storage material of a kind of scope of application especially for measuring a kind of method of hydrogen storage material Pressure-concentration-temperature (PCT) (PCT) curve.
Background technology
The method of mensuration PCT curve commonly used has volumetric method and mass method.
The capacity ratio juris is to extrapolate the variation of hydrogen storage material hydrogen content according to the pressure of the hydrogen storage material sample chamber of constant volume and air storage chamber.Filling hydrogen or putting the variation that hydrogen pressure changes and hydrogen concentration in the hydrogen storage material is calculated in accumulation in the METHOD FOR CONTINUOUS DETERMINATION constant volume obtains the PCT curve according to the state equation of hydrogen.When volumetric determination fills hydrogen process PCT curve, fill hydrogen according to the hydrogen amount of filling of estimation.Owing to fill the hydrogen amount by the Hydrogen Vapor Pressure adjustment sample of adjusting in the constant volume, test more convenient.And measure when putting the PCT curve of hydrogen, control hydrogen desorption capacity by the hydrogen pressure of adjusting in the constant volume of putting.The equipment investment of this method is less, generally all adopts this method to measure the PCT curve of hydrogen storage material.
Mass method is by the suction hydrogen of continuous recording hydrogen storage material or puts the hydrogen mass change and the variation of mutually deserved equalized pressure, thereby obtains the PCT curve.The advantage of mass method is to the direct measurement of being measured as of hydrogen or hydrogen desorption capacity, can be dynamically or measure the PCT curve statically, fill hydrogen and put the hydrogen process very convenient for mensuration.Yet this method equipment investment is huge, needs the little balance of high-resolution quartz oscillation.
Chinese patent application " a kind of pressure, density and temperature performance test method for hydrogen storing alloy, application number: 02109169.2 " reported method only is applicable to the measurement with low pressure or ultralow pressure hydrogen storage material PCT curve.And Chinese patent application " a kind of pressure, density and temperature performance test method for hydrogen storing alloy; application number: 02109169.2 " and " rare metal ", 1997,21 (1), the simple measuring of hydrogen-storage alloy PCT curve, reported method all adopts the perfect condition equation to measure, and this kind method precision is lower.When higher in equilibrium pressure especially, temperature was low, the state equation of actual hydrogen and perfect condition equation had bigger deviation, if the PCT curve that at this moment still adopts the perfect condition equation to measure hydrogen storage material will certainly cause very big error.
Summary of the invention
The object of the present invention is to provide the wide method for accurate testing performance of pressure concentration-temperature of hydrogen storage material of a kind of scope of application.
Technical scheme of the present invention is:
A kind of method of accurate mensuration hydrogen storage material PCT performance comprises the steps:
(1) takes by weighing the hydrogen storage material of quality m, put into the sample chamber;
(2) measure air storage chamber temperature, sample chamber temperature by temperature transmitter, pressure unit is measured the experimental pressure of air storage chamber and sample chamber, and the sample chamber keeps constant temperature;
(3) at first the sample chamber being placed temperature is to open valve under 100～120 ℃, whole test system is vacuumized continue 60～120 minutes; Stop to vacuumize, valve-off supposes that the hydrogen storage content of sample this moment is 0, the gaseous tension 0 of sample chamber;
(4) in air storage chamber, charge into a certain amount of hydrogen and make its pressure remain on 0.001-20MPa, measure and write down the temperature T c of air storage chamber this moment
1, pressure P c
1Open valve, the hydrogen in the hydrogen storage chamber enters sample chamber while hydrogen storage material by connecting tube and begins to inhale hydrogen, and the force value that shows when pressure unit did not change in 10 minutes, think that promptly hydrogen storage material suction hydrogen is saturated under this pressure, record system balancing pressure P this moment b
1And this moment air storage chamber temperature T b
1
(5) valve-off, charged pressure is the hydrogen of 1kPa～20MPa in air storage chamber, measures and write down the temperature T c of air storage chamber this moment
2, pressure P c
2, open valve, the hydrogen in the air storage chamber enters sample chamber while hydrogen storage material and begins to inhale hydrogen, and the force value that shows when pressure unit did not change in 10 minutes, thought that promptly hydrogen storage material suction hydrogen is saturated under this pressure, write down the equalized pressure record Pb of system's this moment
2And this moment air storage chamber temperature T b
2
(6) repeat above-mentioned steps 3,4 processes, it is saturated thoroughly to inhale hydrogen up to hydrogen storage material;
(7) wait to inhale hydrogen saturated after, after valve-off, air storage chamber are emitted the hydrogen of 1e-5～0.01mol, measure the temperature T c of air storage chamber this moment
i, pressure P c
i, open valve, the hydrogen of sample chamber enters air storage chamber hydrogen storage material releasing hydrogen gas simultaneously, and the force value that shows when pressure unit does not change in 10 minutes that to think promptly that under this pressure hydrogen storage material is put hydrogen abundant, record system balancing pressure P this moment b
iAnd this moment air storage chamber temperature T b
i
(8) repeat to put the hydrogen process repeatedly described in the above-mentioned steps 6, fully discharge, write down the temperature of last system balancing pressure and air storage chamber up to the hydrogen of hydrogen storage material;
(9) with the hydrogen under MBWR Equation for Calculating relevant temperature and pressure state compression factor Z (P, T), then according to formula
Calculate the molar weight of balance front and back gaseous hydrogen, calculate its difference ordered series of numbers { Δ n}, this ordered series of numbers being obtained add up and ordered series of numbers cumsum{ Δ n}, is the y axle with equalized pressure Pb then, be that the x axle is drawn suction and put hydrogen PCT curve with hydrogen storage material hydrogen concentration cumsum{ Δ n} * 2/ (m/M); Wherein, R is a gas law constant, and T is an absolute temperature, and P is the pressure of hydrogen, and M is the mole fraction of hydrogen storage material;
(10) whole calculating and drawing course are finished by following program, and whole procedure comprises 5 functions: mbwr-comfactor function, mbwr-eos function, f function, hydron function, hydapi function; Wherein the mbwr-comfactor function is used to calculate the compressibility factor of hydrogen, and input variable is the pressure and temperature of hydrogen, and output variable is the compressibility factor of hydrogen; The mbwr-eos function is used to calculate the density of hydrogen, and input variable is the pressure and temperature of hydrogen, and output variable is the density of hydrogen, and used numerical computation method is a secant method; The f function is that the mbwr equation by above-mentioned hydrogen converts, and its input variable is density, the pressure and temperature of hydrogen, and output variable is a pressure, carries out interative computation for the mbwr-eos function call; The hydron function is used to calculate the molar weight of hydrogen, and its input variable is the temperature and pressure of volume of a container, gas, and output variable is the molar weight of hydrogen; The hydapi function is used to calculate the adding up and ordered series of numbers of mol ratio H/M increment of hydrogen atom and hydrogen storage material molecule, and hydrogen storage material hydrogen and hydrogen desorption capacity, and make the PCT curve map, its input variable is an air storage chamber pressure, sample chamber pressure, the air storage chamber temperature, the sample chamber temperature, the air storage chamber volume, the volume of connecting tube, the volume of sample chamber behind the removal sample volume, the molar weight of sample, its output variable is for inhaling adding up and ordered series of numbers of the mol ratio increment put hydrogen process hydrogen atom and hydrogen storage material molecule, hydrogen process equilibrium pressure ordered series of numbers is put in suction, maximum hydrogen of hydrogen storage material and maximum hydrogen desorption capacity.
Vacuumize in the described step 3, make vacuum tightness reach 10
-1-10
-2Pa.
Described step 8 repeats to put the hydrogen process 20-40 time described in the above-mentioned steps 6.
The invention has the beneficial effects as follows:
1, the present invention is owing to having considered the influence of air storage chamber temperature fluctuation to experimental result, so even the air storage chamber of equipment part can not realize constant temperature, PCT curve that its test obtains is still true and reliable in program.
2, the present invention has good practical value, and it makes equipment become simple and easy operating, has higher confidence level simultaneously when test such as CNT, vanadium etc. has the PCT curve of hydrogen storage material of high equilibrium pressure.
3, the present invention can obviously improve testing efficiency, and it is all finished whole data processing and drawing course automatically by computing machine, and the operator only needs related pressure and temperature data inserted and gets final product.
Description of drawings
Fig. 1 is the simple and easy synoptic diagram of the inventive method operative installations; Among the figure, 1 temperature transmitter; 2 pressure units; 3 air storage chambers; 4 valves; 5 connecting tubes; 6 sample chambers; 7 hydrogen storage materials; 8 temperature transmitters.
Fig. 2 is before valve 4 is opened among Fig. 1, the molar weight of hydrogen in the each several part.
Fig. 3 opens the back hydrogen storage material for valve 4 among Fig. 1 and inhales and put hydrogen and reached balance, the molar weight of hydrogen in the each several part.
The LaNi of Fig. 4 for using the inventive method to obtain
5Inhale 40 ℃ the first time and put hydrogen PC curve.
Fig. 5 a-d is the MATLAB program flow diagram.
Embodiment
The inventive method operative installations as shown in Figure 1, this device comprises temperature transmitter 1, pressure unit 2, air storage chamber 3, valve 4, connecting tube 5, sample chamber 6, hydrogen storage material 7, temperature transmitter 8.Temperature transmitter 1, pressure unit 2 are housed on the air storage chamber 3; Temperature transmitter 8 is housed on the sample chamber 6, hydrogen storage material 7 is housed in it; Air storage chamber 3 links to each other by connecting tube 5 with sample chamber 6, and connecting tube 5 is provided with valve 4.
The invention provides a kind of method of accurate mensuration hydrogen storage material PCT performance, comprise the steps:
1, takes by weighing the hydrogen storage material of certain mass m, put into the sample chamber;
2, measure air storage chamber temperature, sample chamber temperature by temperature transmitter 1, pressure unit 2 is measured the experimental pressure of air storage chamber 3 and sample chamber 6, and sample chamber 6 keeps constant temperature;
3, at first the sample chamber is placed under the high temperature (about 100 ℃) to open valve 4, by the direct connection vacuum pump whole test system is vacuumized and continue 60～120 minutes, make vacuum tightness reach 10
-1Pa.Stop to vacuumize, valve-off 4 supposes that the hydrogen storage content of sample this moment is 0, the gaseous tension 0 of sample chamber;
4, in air storage chamber 3, charge into the hydrogen (pressure is 0.01-20MPa) of certain pressure, measure and write down the temperature T c of air storage chamber 3 this moment
1, pressure P c
1Open valve 4, hydrogen in the hydrogen storage chamber 3 enters sample chamber 6 while hydrogen storage material 7 by connecting tube 5 and begins to inhale hydrogen, and the force value that shows when pressure unit did not have variation to think that promptly hydrogen storage material suction hydrogen is saturated under this pressure in 10 minutes, write down system balancing pressure P b this moment
1(this force value be the pressure of sample chamber also be the pressure of air storage chamber) and this moment air storage chamber temperature T b
1
5, valve-off 4, and (pressure is 1kPa～20MPa), measures the also temperature T c of record air storage chamber this moment to charge into the hydrogen of certain pressure in air storage chamber
2, pressure P c
2Open valve 4, hydrogen in the air storage chamber enters sample chamber while hydrogen storage material 7 and begins to inhale hydrogen, and the force value that shows when pressure unit did not have variation to think that promptly hydrogen storage material suction hydrogen is saturated under this pressure in 10 minutes, and the equalized pressure that writes down system's this moment writes down Pb
2(this force value be the pressure of sample chamber also be the pressure of air storage chamber) and this moment air storage chamber temperature T b
2
6, repeat above-mentioned steps 3,4 processes, it is saturated thoroughly to inhale hydrogen up to hydrogen storage material;
7, wait to inhale hydrogen saturated after, valve-off 4, air storage chamber are emitted a certain amount of hydrogen and (behind the 1e-5～0.01mol), are measured the temperature T c of air storage chamber this moment
i, pressure P c
i, open valve 4, the hydrogen of sample chamber enters air storage chamber hydrogen storage material releasing hydrogen gas simultaneously, and the force value that shows when pressure unit does not change in 10 minutes that to think promptly that under this pressure hydrogen storage material is put hydrogen abundant, record system balancing pressure P this moment b
i(this force value be the pressure of sample chamber also be the pressure of air storage chamber) and this moment air storage chamber temperature T b
i
8, the hydrogen process of putting described in the repeating step 6 repeatedly (present embodiment is 20 times) fully discharges up to the hydrogen of hydrogen storage material, writes down the temperature of last system balancing pressure and air storage chamber;
9, with the equation MBWR equation of the description hydrogen virtual condition the best of generally acknowledging at present, calculate corresponding to the hydrogen uniform temperature and pressure state under compress factor Z (P, T), then according to formula
Calculate the molar weight of balance front and back gaseous hydrogen, calculate its difference ordered series of numbers { Δ n}, this ordered series of numbers obtained add up and ordered series of numbers cumsum{ Δ n}, be the y axle with equalized pressure Pb then, with hydrogen storage material hydrogen concentration cumsum{ Δ n} * 2/ (m/M) (M: be that the x axle is drawn to inhale and put hydrogen PCT curve the mole fraction of hydrogen storage material);
10, whole calculating and drawing course are finished by working out the MATLAB program voluntarily.
The present invention is owing to having considered the influence of air storage chamber temperature fluctuation to experimental result, so even the air storage chamber of equipment part can not realize constant temperature, PCT curve that its test obtains is still true and reliable in program.This feature has good practical value, and it makes equipment become simple and easy operating, has higher confidence level simultaneously when test such as CNT, vanadium etc. has the PCT curve of hydrogen storage material of high equilibrium pressure.
What the present invention adopted is volumetric method, i.e. suction hydrogen by the continuous recording hydrogen storage material or put the each several part Hydrogen Vapor Pressure of hydrogen process and temperature is extrapolated the hydrogen of corresponding different hydrogen pressure hydrogen storage material according to the MBWR equation obtains the PCT curve.Key problem in technology is the calculating that how realizes compressibility factor by computer programming.Very complicated equation of MBWR equation, its form is:
P＝ρRT+ρ
2(N
0T+N
1T
1/2+N
2+N
3/T+N
4/T
2)
+ρ
3(N
5T+N
6+N
7/T+N
8/T
2)
+ρ
4(N
9T+N
10+N
11/T)+ρ
5(N
12)
+ρ
6(N
13/T+N
14/T
2)+ρ
7(N
15/T)
+ρ
8(N
16/T+N
17/T
2)+ρ
9(N
18/T
2)
+ρ
3(N
19/T
2+N
20/T
3)exp(γρ
2)
+ρ
5(N
21/T
2+N
22/T
4)exp(γρ
2)
+ρ
7(N
23/T
2+N
24/T
3)exp(γρ
2)
+ρ
9(N
25/T
2+N
26/T
4)exp(γρ
2)
+ρ
11(N
27/T
2+N
28/T
3)exp(γρ
2)
+ρ
13(N
29/T
2+N
30/T
3+N
31/T
4)exp(γρ
2)
N wherein
0～N
31, γ is for describing the parameter of hydrogen character, and ρ is a hydrogen density, and R is a gas law constant, and T is an absolute temperature, and P is the pressure of hydrogen, and what this equation was described is the relation of Hydrogen Vapor Pressure and its density and temperature.Can measure the pressure and the temperature of gas by pressure unit and temperature transmitter, realize that by programming computing machine calculates hydrogen density ρ automatically, the numerical computation method that is adopted is a secant method.Then, according to formula
Calculate corresponding to this pressure, and the hydrogen compression factor Z under the temperature (P, T).Before can getting valve 4 and open by Fig. 2 in the air storage chamber hydrogen molar weight be n
1i, the hydrogen molar weight is n in the connecting tube
2i, hydrogen molar weight n in the sample chamber
3i, after can getting valve 4 and open by Fig. 3, when suction put the hydrogen process when reaching balance in the air storage chamber hydrogen molar weight be n
4i, the hydrogen molar weight is n in the connecting tube
5i, the hydrogen molar weight is n in the sample chamber
6i, then the sucking/placing hydrogen amount of hydrogen storage material is
When
The time, the suction hydrogen of hydrogen storage material, when
The time, hydrogen storage material put hydrogen.Because in the actual measurement process, hydrogen storage material is inhaled and to be put hydrogen balance and charge and discharge time interval very short (less than one minute) of hydrogen process to air storage chamber next time, and ambient temperature fluctuates very little, so can draw tc
I+1=tb
i, the temperature the when meaning of this equation is this air storage chamber temperature that records with the balance that recorded last time equates (i be one more than or equal to 1 variable).In addition, because last hydrogen storage material inhales and puts hydrogen and reach balance, so can think that the gaseous tension of sample chamber remains unchanged before filling hydrogen, i.e. Py next time
I+1=Pb
i, the pressure the when meaning of this equation is this sample chamber pressure that records with the balance that recorded last time equates (i be one more than or equal to 1 variable).Through filling hydrogen and putting the hydrogen process repeatedly, relevant temperature and pressure data are handled to obtain hydrogen storage material sucking/placing hydrogen amount ordered series of numbers
This ordered series of numbers is added up and processing obtains one and adds up and ordered series of numbers cumsum
This be one about the adding up and ordered series of numbers of hydrogen molecule, and in the actual test in the PCT curve map its horizontal ordinate be the mol ratio H/M of hydrogen atom and hydrogen storage material molecule, so
Y in addition
i=Pb
i, be horizontal ordinate with xi, yi is that the ordinate mapping just obtains the PCT curve map.
As shown in Figure 2, before valve 4 is opened among Fig. 1, the molar weight of hydrogen in the each several part; As shown in Figure 3, valve 4 is opened the back hydrogen storage material and is inhaled and to put hydrogen and reached balance, the molar weight of hydrogen in the each several part among Fig. 1.
MATLAB program flow diagram shown in Fig. 5 a-d, whole procedure comprise 5 functions: mbwr-comfactor function, mbwr-eos function, f function, hydron function, hydapi function.Wherein, shown in Fig. 5 c, the mbwr-comfactor function is used to calculate the compressibility factor of hydrogen, and input variable is the pressure and temperature of hydrogen, and output variable is the compressibility factor of hydrogen; Shown in Fig. 5 d, the mbwr-eos function is used to calculate the density of hydrogen, and input variable is the pressure and temperature of hydrogen, and output variable is the density of hydrogen, and used numerical computation method is a secant method; Shown in Fig. 5 d, the f function is that the mbwr equation by above-mentioned hydrogen converts, and its input variable is density, the pressure and temperature of hydrogen, and output variable is a pressure, and this function does not have physical significance, and purpose is to carry out interative computation for the mbwr-eos function call; Shown in Fig. 5 b, the hydron function is used to calculate the molar weight of hydrogen, and its input variable is a volume of a container, the temperature and pressure of gas, and output variable is the molar weight of hydrogen; Shown in Fig. 5 a, the hydapi function is used to calculate the adding up and ordered series of numbers of mol ratio H/M increment of hydrogen atom and hydrogen storage material molecule, and hydrogen storage material hydrogen and hydrogen desorption capacity, and makes the PCT curve map.Its input variable is the volume of air storage chamber pressure, sample chamber pressure, air storage chamber temperature, sample chamber temperature, air storage chamber volume, connecting tube, the volume of removing sample chamber behind the sample volume, the molar weight of sample, and its output variable is for inhaling adding up and ordered series of numbers, inhaling and put hydrogen process equilibrium pressure ordered series of numbers, hydrogen storage material maximum hydrogen and maximum hydrogen desorption capacity of the mol ratio increment of putting hydrogen process hydrogen atom and hydrogen storage material molecule.
It below is the MATLAB program of whole computation process.
This subprogram is used to calculate the compressibility factor of hydrogen:
function?z＝mbwr_comfactor(P，T)
％The?32-term?equation?of?state；
％Based?on?the?Modified?Bennedict-webb-rubin?equation?of?state；
％P--kPa；
％T--k；
The compressibility factor that % might calculate under extreme environment is inaccurate;
% is only at conventional temperature 273.15～573.15k, and under conventional pressure 0.001～100Mpa, the compression that this program calculates is reliably because of %, and the PCT curve test environment of hydrogen storage material is contained in this scope.
The numerical computation method that % uses is secant method.
R＝8.314472；
ro＝mbwr_eos(P，T)；
z＝P./ro./R./T；
function?ro＝mbwr_eos(P，T)
R＝8.31447；
ro0＝0.002；
ro1＝P./R./T；
y＝1；
while?ab(y)＞1e-7
ro2＝(ro0.*feval(@f，ro1，P，T)-ro1.*feval(@f，ro0，P，T))./...(feval(@f，ro1，P，T)-feval(@f，ro0，P，T))；
ro0＝ro1；
ro1＝ro2；
y＝feval(@f，ro1，P，T)；
end
ro＝ro1；
function?y＝f(ro，P，T)
rr＝0.00831434；
gm＝-0.41000000E-02；
g0＝.4675528393416E-04；g1＝.4289274251454E-02；g2＝.5164085596504E-01；
g3＝.2961790279801E+00；g4＝-.3027194968412E+01；g5＝.1908100320379E-05；
g6＝-.1339776859288E-03；g7＝.3056473115421E-01；g8＝.5161197159532E+01；
g9＝.1999981550224E-07；g10＝.2896367059356E-04；g11＝-.2257803939041E-02；
g12＝-.2287392761826E-06；g13＝.2446261478645E-05；g14＝-.1718181601119E-03；
g15＝-.5465142603459E-07；g16＝.4051941401315E-09；g17＝.1157595123961E-06；
g18＝-.1269162728389E-08；g19＝-.4983023605519E+01；g20＝-.1606676092098E+02；
g21＝-.1926799185310E-01；g22＝.9319894638928E+00；g23＝-.3222596554434E-04；
g24＝.1206839307669E-03；g25＝-.3841588197470E-07；g26＝-.4036157453608E-05；
g27＝-.1250868123513E-10；g28＝.1976107321888E-09；g29＝.2411883474011E-13；
g30＝-.4127551498251E-13；g31＝.8917972883610E-12；
d0＝ro；d1＝ro.^2；d2＝ro.^3；d3＝ro.^4；d4＝ro.^5；d5＝ro.^6；d6＝ro.^7；d7＝ro.^8；d8＝ro.^9；
d9＝ro.^10；d10＝ro.＾11；d11＝ro.＾12；d12＝ro.^13；
t0＝sqrt(T)；t1＝T.^2；t2＝T.^3；t3＝T.^4；
f＝exp(gm.*d1)；
b0＝d1.*T；b1＝d1.*t0；b2＝d1；
b3＝d1./T；b4＝d1./t1；b5＝d2.*T；
b6＝d2；b7＝d2./T；b8＝d2./t1；
b9＝d3.*T；b10＝d3；b11＝d3./T；
b12＝d4；b13＝d5./T；b14＝d5./t1；
b15＝d6./T；b16＝d7./T；b17＝d7./t1；
b18＝d8./t1；b19＝d2.*f./t1；b20＝d2.*f./t2；
b21＝d4.*f./t1；b22＝d4.*f./t3；b23＝d6.*f./t1；
b24＝d6.*f./t2；b25＝d8.*f./t1；b26＝d8.*f./t3；
b27＝d10.*f./t1；b28＝d10.*f./t2；b29＝d12.*f./t1；
b30＝d12.*f./t2；b31＝d12.*f./t3；
p＝(b0.*g0+b1.*g1+b2.*g2+b3.*g3+b4.*g4+b5.*g5+b6.*g6+b7.*g7+b8.*g8+b9.*g9...+b10.*g10+b11.*g11+b12.*g12+b13.*g13+b14.*g14+b15.*g15+b16.*g16+b17.*g17...+b18.*g18+b19.*g19+b20.*g20+b21.*g21+b22.*g22+b23.*g23+b24.*g24+b25.*g25...+b26.*g26+b27.*g27+b28.*g28+b29.*g29+b30.*g30+b31.*g31+rr.*d0.*T).*1000；
y＝p-P；
This subprogram is used to calculate the molar weight of hydrogen:
function?n＝hydron(P，t，V)
% is used to ask the true molar weight of hydrogen
％P--kPa；
％t--℃；
％V-ml；
％n--mol
When % was 0kPa when Hydrogen Vapor Pressure, its molar weight was 0
R＝8.314472；
T＝t+273.15；
J＝find(P＝＝0)；
n＝P.*V./1000./R./T./mbwr_comfactor(P，T)；
n(J)＝0；
This subprogram is used to calculate the adding up and ordered series of numbers of mol ratio H/M increment of hydrogen atom and hydrogen storage material molecule, and hydrogen storage material hydrogen and hydrogen desorption capacity, and makes the PCT curve map.
function[cumlsum，cumlsuma，cumlsumd，Pb，Pba，Pbd，maxa，maxd]＝hydapi(Pc，Py，tc，ty，Vc，Vy1，Vy2，nm)％[cumlsum?cumlsuma?cumlsund?Pb?Pba?Pbd?maxa
％maxd]＝hydapi(Pc，Py，tc，ty，Vc，Vy1，Vy2，nm)；
The air storage chamber pressure that writes down in the %Pc-test process, unit are kPa;
The sample chamber pressure that writes down in the %Py-test process, unit are kPa;
The temperature of the air storage chamber that writes down in the %tc-test process, unit is ℃;
The temperature of the sample chamber of writing down in the %ty-test process, unit is ℃;
The volume of %Vc-air storage chamber, unit are ml;
The volume of %Vy1-connecting tube, unit are ml;
The volume of sample chamber behind the %Vy2-removal sample volume, unit is ml;
The molar weight of %nm-sample, unit is mol;
%cumlsum-comprises the adding up and ordered series of numbers of mol ratio H/M increment of the hydrogen atom inhaling hydrogen and put the hydrogen process and hydrogen storage material molecule;
%cumlsuma-only inhales the adding up and ordered series of numbers of mol ratio H/M increment of the hydrogen atom of hydrogen process and hydrogen storage material molecule;
%cumlsumd-is only put the adding up and ordered series of numbers of mol ratio H/M increment of the hydrogen atom of hydrogen process and hydrogen storage material molecule;
The %Pb-hydrogen storage material is inhaled and is put the equilibrium pressure ordered series of numbers of hydrogen process;
The %Pba-hydrogen storage material is inhaled the equilibrium pressure ordered series of numbers of hydrogen process;
The %Pbd-hydrogen storage material is put the equilibrium pressure ordered series of numbers of hydrogen process;
The maximum hydrogen of %maxa-hydrogen storage material;
The maximum hydrogen desorption capacity of %maxb-hydrogen storage material;
J=length (Py); % obtains the length of Py array;
% presses array according to equation Py (i+1)=Pb (i) equilibrium establishment;
Pb＝zeros(J-1，1)；
for?i＝1:J-1
Pb(i)＝Py(i+1)；
end
% sets up the equilibrium pressure array of inhaling the hydrogen process;
[CI]＝max(Pb)；
Pba＝zeros(I，1)；
fori＝1:I
Pba(i)＝Pb(i)；
end
% sets up the equilibrium pressure array of putting the hydrogen process;
Pbd＝zeros(J-I，1)；
for?i＝1:J-I
Pbd(i)＝Pb(J-i)；
end
% sets up the array of the sample chamber pressure that is used for the use of actual computation process;
Py1＝zeros(J-1，1)；
for?i＝1:J-1
Py1(i)＝Py(i)；
end
% sets up the array of the preceding air storage chamber temperature of molecular balance that is used for the actual computation process;
tc1＝zeros(J-1，1)；
for?i＝1:J-1
tc1(i)＝tc(i)；
end
% sets up the array of air storage chamber temperature behind the molecular balance that is used for the actual computation process according to equation tc (i+1)=tb (i);
tb＝zeros(J-1，1)；
for?i＝1:J-1
tb(i)＝tc(i+1)；
end
% calculates the sucking/placing hydrogen amount array of inhaling the hydrogen storage material of putting the hydrogen process;
N1=hydron (Pc, tc1, Vc); The molar weight of Gaseous Hydrogen molecule in the air storage chamber before the % reaction;
N2=hydron (Py1, tc1, Vy1); The molar weight of Gaseous Hydrogen molecule in the connecting tube before the % reaction;
N3=hydron (Py1, ty, Vy2); % reacts the molar weight of Gaseous Hydrogen molecule in the preceding sample chamber;
N4=hydron (Pb, tb, Vc); The molar weight of Gaseous Hydrogen molecule in the air storage chamber after the % balance;
N5=hydron (Pb, tb, Vy1); The molar weight of Gaseous Hydrogen molecule in the connecting tube after the % balance
N6=hydron (Pb, ty, Vy2); The molar weight of Gaseous Hydrogen molecule in the sample chamber after the % balance;
Detan=n1+n2+n3-n4-n5-n6; The % hydrogen storage material is inhaled and is put the hydrogen molar weight;
cumlsum＝cumsum(detan).*2./nm；
cumlsuma＝zeros(I，1)；
for?i＝1:I
cumlsuma(i)＝cumlsum(i)；
end
cumlsumd＝zeros(J-I，1)；
for?i＝1:J-I
cumlsumd(i)＝cumlsum(J-i)；
end
maxa＝cumlsum(I)；
maxd＝maxa-cumlsum(J-1)；
plot(cumlsum，Pb)；
Preparation hydrogen storage material LaNi
5Alloy button ingot is pressed the design mix preparation, and used metal purity (at%) is La 99.3%, and Ni 99.9%.Above-mentioned raw materials is cleaned with ultrasonator, press the design mix counterweight afterwards, the material for preparing is placed water cooled copper mould; under argon gas atmosphere protection, melting in electric arc furnaces, in fusion process with alloy turn-over remelting five times; carry out electromagnetic agitation simultaneously, to guarantee the homogeneity of alloy.After the melting alloy pig is enclosed in the vitreosil pipe, puts into heat-treatment furnace, be warming up to 1100 ℃ of insulations with stove and quench after 8 hours.On this integral test system, carry out LaNi then
5The hydrogen storage performance test of hydrogen storage material, used hydrogen purity 99.999%.The sample that 1～2 gram is ground is put into reactor, and sample vacuumizes (to 10 with mechanical pump in the time of 40 ℃
-2Pa) after 50～60 minutes, in device shown in Figure 1, test by the inventive method.
The LaNi of Fig. 4 for using the inventive method to obtain
5Inhale 40 ℃ the first time and put hydrogen pressure-composition (P-C) curve map.Maximum hydrogen is 6.2961, and maximum hydrogen desorption capacity is 5.841.As seen from the figure, the PCT curve map that utilizes the perfect condition equation to record obviously can not react truth.
Adopt the present invention to can be used as the hydrogen storage material performance testing equipment method of testing in (Chinese invention patent application, application number 200410050594.3, October 15 2004 applying date).
Claims (3)
1, a kind of method for accurate testing performance of pressure concentration-temperature of hydrogen storage material is characterized in that comprising the steps:
(1) takes by weighing the hydrogen storage material of quality m, put into the sample chamber;
(2) measure air storage chamber temperature, sample chamber temperature by temperature transmitter, pressure unit is measured the experimental pressure of air storage chamber and sample chamber, and the sample chamber keeps constant temperature;
(3) at first the sample chamber being placed temperature is to open valve under 100～120 ℃, whole test system is vacuumized continue 60～120 minutes; Stop to vacuumize, valve-off supposes that the hydrogen storage content of sample this moment is 0, the gaseous tension 0 of sample chamber;
(4) in air storage chamber, charge into a certain amount of hydrogen and make its pressure remain on 0.001-20MPa, measure and write down the temperature T c of air storage chamber this moment
1, pressure P c
1Open valve, the hydrogen in the hydrogen storage chamber enters sample chamber while hydrogen storage material by connecting tube and begins to inhale hydrogen, and the force value that shows when pressure unit did not change in 10 minutes, think that promptly hydrogen storage material suction hydrogen is saturated under this pressure, record system balancing pressure P this moment b
1And this moment air storage chamber temperature T b
1
(5) valve-off, charged pressure is the hydrogen of 1kPa～20MPa in air storage chamber, measures and write down the temperature T c of air storage chamber this moment
2, pressure P c
2, open valve, the hydrogen in the air storage chamber enters sample chamber while hydrogen storage material and begins to inhale hydrogen, and the force value that shows when pressure unit did not change in 10 minutes, thought that promptly hydrogen storage material suction hydrogen is saturated under this pressure, write down the equalized pressure record Pb of system's this moment
2And this moment air storage chamber temperature T b
2
(6) repeat above-mentioned steps 3,4 processes, it is saturated thoroughly to inhale hydrogen up to hydrogen storage material;
(7) wait to inhale hydrogen saturated after, after valve-off, air storage chamber are emitted the hydrogen of 1e-5～0.01mol, measure the temperature T c of air storage chamber this moment
i, pressure P c
i, open valve, the hydrogen of sample chamber enters air storage chamber hydrogen storage material releasing hydrogen gas simultaneously, and the force value that shows when pressure unit does not change in 10 minutes that to think promptly that under this pressure hydrogen storage material is put hydrogen abundant, record system balancing pressure P this moment b
iAnd this moment air storage chamber temperature T b
i
(8) repeat to put the hydrogen process repeatedly described in the above-mentioned steps 6, fully discharge, write down the temperature of last system balancing pressure and air storage chamber up to the hydrogen of hydrogen storage material;
(9) with the hydrogen under MBWR Equation for Calculating relevant temperature and pressure state compression factor Z (P, T), then according to formula
Calculate the molar weight of balance front and back gaseous hydrogen, calculate its difference ordered series of numbers { Δ n}, this ordered series of numbers being obtained add up and ordered series of numbers cumsum{ Δ n}, is the y axle with equalized pressure Pb then, be that the x axle is drawn suction and put hydrogen PCT curve with hydrogen storage material hydrogen concentration cumsum{ Δ n} * 2/ (m/M); Wherein, R is a gas law constant, and T is an absolute temperature, and P is the pressure of hydrogen, and M is the mole fraction of hydrogen storage material;
(10) whole calculating and drawing course are finished by following program, and whole procedure comprises 5 functions: mbwr-comfactor function, mbwr-eos function, f function, hydron function, hydapi function; Wherein the mbwr-comfactor function is used to calculate the compressibility factor of hydrogen, and input variable is the pressure and temperature of hydrogen, and output variable is the compressibility factor of hydrogen; The mbwr-eos function is used to calculate the density of hydrogen, and input variable is the pressure and temperature of hydrogen, and output variable is the density of hydrogen, and used numerical computation method is a secant method; The f function is that the mbwr equation by above-mentioned hydrogen converts, and its input variable is density, the pressure and temperature of hydrogen, and output variable is a pressure, carries out interative computation for the mbwr-eos function call; The hydron function is used to calculate the molar weight of hydrogen, and its input variable is the temperature and pressure of volume of a container, gas, and output variable is the molar weight of hydrogen; The hydapi function is used to calculate the adding up and ordered series of numbers of mol ratio H/M increment of hydrogen atom and hydrogen storage material molecule, and hydrogen storage material hydrogen and hydrogen desorption capacity, and make the PCT curve map, its input variable is an air storage chamber pressure, sample chamber pressure, the air storage chamber temperature, the sample chamber temperature, the air storage chamber volume, the volume of connecting tube, the volume of sample chamber behind the removal sample volume, the molar weight of sample, its output variable is for inhaling adding up and ordered series of numbers of the mol ratio increment put hydrogen process hydrogen atom and hydrogen storage material molecule, hydrogen process equilibrium pressure ordered series of numbers is put in suction, maximum hydrogen of hydrogen storage material and maximum hydrogen desorption capacity.
2, according to the described method for accurate testing performance of pressure concentration-temperature of hydrogen storage material of claim 1, it is characterized in that: vacuumize in the described step 3, make vacuum tightness reach 10
-1-10
-2Pa.
3, according to the described method for accurate testing performance of pressure concentration-temperature of hydrogen storage material of claim 1, it is characterized in that: described step 8 repeats to put the hydrogen process 20-40 time described in the above-mentioned steps 6.
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