DEVELOPMENT of ONE AMPERE-HOUR HEAT Sterl LIZABLE SILVER-ZINC CELL
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JANUARY 1967 REPORT SM-4910942 DEVELOPMENT OF ONE AMPERE-HOUR HEAT STERl LIZABLE SILVER-ZINC CELL PROGRESS REPORT FOR PERIOD 1 OCTOBER TO 31 DECEMBER 1966 GPO PRICE $ UNDER CONTRACT HAS 2-3819 CFSTl PRICE(S) $ Hard copy (HC) 1. m I / Microfiche (MF) I I I ff653 Julv65 AST R 0 P 0W E R LA6 0 RAT0RY I 2121 CAMPUS DRIVE NEWPORT BEACH, CALIFORNIA 8 MISSILE 8c SPACE SYSTEMS DIVISION DOUGLAS AIRCRAFT COMPANY, INC. I S A N TA M 0 N I C A/ C A L I FOR N I A I I DffUG 0 t Report SM-49109-Q2 DEVELOPMENT OF ONE AMPERE-HOUR HEAT STERILIZABLE SILVER - ZINC CELL Progress Report for Period 1 October to 31 December 1966 Contract NAS 2-3819 I By: Approved by: I I A. Himy C. Berger, Ph.B(. Senior Research Scientist Head, Electrochemistry Department MISSILE & SPACE SYSTEMS DIVISION ASTROPOWER LABORATORY Douglas Aircraft Company, Inc. Newport Beach, California I I TABLE OF CONTENTS 1.0 INTRODUCTION AND SUMMARY 1 I 2.0 MECHANICAL TESTING 2 2.1 Terminal Seal 2 2.2 Cover-to-Case Seal 2 I 2.3 Other Concepts - Cylindrical Cell 7 2.3. 1 Case and Cover Design 7 2. 3. 2 Cell Design and Assembly 14 1 2.3.3 Separator Cup 14 2. 3.4 Sealing of Cell 14 I 3.0 ELECTRICAL 18 3. 1 Wafer Configuration Design 18 1 3.2 Separator Box Design 26 3.2. 1 First Run 26 3.2.2 Second Run 26 I 3. 3 Cylindrical Cell 30 4.0 MISCELLANEOUS 33 I 4.1 Inorganic Separators 33 4.2 Interseparator 33 4.2. 1 KT 33 I 4.2. 2 Coating 4561-7 33 I 5.0 CONCLUSIONS 34 6.0 WORK PLANNED 35 1 REFERENCES 36 a I I 1 s I SM-49 109-Q2 ii I 1 1 LIST OF ILLUSTRATIONS 1 Terminal-to-Cover Seal Design #3 3 I 2 Cover - to -Case Sealing 4 3 Cylindrical Cell, Design #1 8 1 4 Cylindrical Cell, Design #2 9 5 Cylindrical Cell, Design #3 10 6 Cylindrical Cell, Design #4 11 1 7 Cylindrical Cell, Design #5 12 8 Cylindrical Cell, Design #6 13 I 9 Typical cylindrical Cell Assembly 15 10 Separator Cup 16 1 11 Flat Separator Before Sterilization, After Sterilization, and After Cycling 19 12 Plastic Cell Assembly 20 1 13 Standard Design: Cell Sterilized, Unformed - Nominal Capacity: 2 Ah 22 I 14 Standard Design Cell Sterilized After Formation and Discharge - Nominal Capacity: 2 Ah 23 15 Characteristics of Cell Sterilized, Unformed, on Automatic I Cycling 24 16 Characteristics of Cell Sterilized, Unformed, on Automatic Cycling 25 I 17 Separator Box 27 18 Sterilized Separator Box 28 1 19 Box Design - Nominal Capacity: 1 Ah 29 20 Box Design: Cell Sterilized, Unformed - Nominal Capacity: 1 1 Ah 31 21 Box Design Cell Sterilized After Formation and Discharge - I Nominal Capacity: 1 Ah 32 1 1 1 I SM-49 109-Q2 iii 1 1 1.0 INTRODUCTION AND SUMMARY 1 The salient achievement of this period was the demonstration of the capability of a silver-zinc cell using inorganic separators to be sterilized, 1 whether in the unformed state, or in a discharged state after formation, and to run successfully on its duty cycle. To establish the extent of their relia- 1 bility, the cells were automatically cycled on a simulated low-orbital flight of 60-minute period and yielded up to 274 cycles. 1 As expected, the cells, which were sterilized in sealed vessels, ex- hibited different pressures depending on their presterilization state of forrna- I tion. The preformed cell ran 27 psig higher than the unformed cell and developed a very high hydrogen content. However, higher amalgamation of the zinc in preformed cells will help reduce hydrogen generation and probably I the pressure margin. 1 Different approaches were considered for establishing a seal. The rectilinear case, made of polysulfone, cannot be reliably sealed with solvent or epoxy cements. Ultrasonic welding has been tried, showed encouraging I results, and will be pursued as well as hot-gas welding. As a back-up to the rectilinear case, a cylindrical configuration is 1 following a parallel course. Preliminary seal testing showed the feasibility of achieving a hermetic seal capable of withstanding the sterilization procedure I of 145OC for 108 hours. A cylindrical separator cup made of inorganic ma- terial was developed for the electrochemical cell design intended for this type 1 of configuration. I I I 1 1 1 1 I 2.0 MECHANICAL TESTING 2. 1 Terminal Seal As shown in Figure 1, a new design terminal seal (Design #3) to be used as a back-up was tested under sterilization conditions in the special test fixture described in the first quarterly report. The design consists of a teflon circular wedge pressed into a countersink by the terminal base when the terminal top is tightened with a nut. Extra sealing was provided with epoxy resin, filling all void space around the terminal body as well as the top and bottom. The terminal assembly held a pressure of 48 to 53 psig at 145OC for 119 hours, after which the test was discontinued. The terminal top did not show any traces of alkali. With teflon etching, it is expected that the bonding will be better and will improve the reliability of the seal over a long period. 2.2 Cover-to-Case Seal More work was done on the cover-to-case sealing. Figure 2 depicts another type of sealing. The cell case is held in an inverted position, fitting into the cover where a fresh layer of epoxy resin 1/8 inch thick has been poured. The epoxy is also spread between the junction surfaces of the case and cover until it is squeezed out. Fiberglas tape (3M Scotch 361) impregnated with fresh epoxy is wrapped around the case at the junction line. Before assembling the case, the holes for terminals were plugged and a polyethylene tube was temporarily fitted into the filling hole to leave the opening free for adapting the pressure devices. After curing the epoxy at 12OoC for two to three hours, the assembly was subjected to 1450 C. After 10 hours, it developed a leak around the pressure fitting in the center hole at about 16 psig. The test was repeatedmore carefully. The case was partly filled with 45% KOH, fitted with a pressure gauge and placed in an oven at 145OC. After holding a constant pressure of 14 psig for 20 hours, it developed a minute leak and the pressure gradually dropped to 0 over the next 20 hours. A minute crack was found on the junction line. SM-49 l09-Q2 2 I 1 1 I 8-32 Screw Terminal ' I I I 1 I I\ I I Electrode Leads to Go Through Hollow Terminal I -(Crimp or Solder) 1 1 I Figure 1. Terminal-to-Cover Seal Design #3 I 1 3 i I Epoxy Impregnated Fiberglas Tape Polyethylene Tube Into Filling Hole ram Figure 2. Cover-to-Case Sealing SM-49109422 4 I This type of seal does not appear to be reliable for several I reasons: The case and cover presently tested are machined out of polysulfone sheet. This operation introduces stresses in the material and the steriliza- 1 tion temperature certainly enhances its aptitude to crazing. On the other hand, the epoxy sealant does not provide a good surface bond to polysulfone, I mainly at high temperature and in an alkaline medium. The pressures en- countered during sterilization are not so high as to promote a catastrophic mechanical failure of the seal. The failure is more related to a wear-out OF I fatigue of the bonded and bonding materials, due to prolonged exposure to high temperature and alkaline medium. 1 Rather than trying to improve this approach on this limited pro- gram, it was decided to scan rapidly other alternatives. I In order to eliminate the effect of machining on polysulfone, tests will be carried out on molded five ampere-hour cases and covers R presently available from another NASA program. (2) Only Polysulfone P-1700 is readily available. All PPO grades I under consideration are still in process, but may not be available for test for some time. 1 Other sealing methods to be investigated are ultrasonic welding I and hot-gas welding. A horn for ultrasonic welding was fabricated to fit the molded five ampere-hour case and cover. Several polysulfone cases were welded at I various settings (three cases per setting): I Weld Time Hold Time Horn Pressure Identification (sec) (set) (1bs 1 #1 1.25 0. 50 60 I #3 1.00 0. 50 60 I #5 0.80 0.50 69 1 1 I 5 I 1 The cases were pressure-tested in succession as follows: 1 (Any subsequent test was done only on cases having passed the previous test. ) 1. Pressure tested at 10 psig for 5 minutes at 25OC I 2. Pressure tested at 50 psig for 5 minutes at 25OC 3. Submitted to 145OC ambient for 16 hours, then pressure I tested at 50 psig for 5 minutes at 25OC. At this point all cases were potted with epoxy (Allbond) along all the welded I seams to plug leakage paths. The epoxy would be used as a sealant rather than an adhesive since the ultrasonic weld seemed to offer a strong joint, but I possibly an incomplete seal. The cases were put back on test as follows: I 4, Pressure tested at 50 psig for 5 minutes at 25OC 5.