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   The batteries industry is in a period of rapid, and possibly irreversible,
   change. The supremacy of existing...
     Axion Power International invented
   a new PbC technology. The lead anode        Scientists discovered that ...
                                                       SCAMPER for Li-ion batteries
       THE POWER FROM         ...
   SCAMPER for lithium air batteries
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Scamper 2010


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SCAMPER - a new ideas machine for the battery business

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Scamper 2010

  1. 1. OPINION The batteries industry is in a period of rapid, and possibly irreversible, change. The supremacy of existing technologies is being challenged amid a flood of new chemistries and new ways of using old chemistries. Industry experts Rangasamy Pitchai and Mark Mack look at a fascinating technique to take this flood of ideas to the next level. SCAMPER — a new ideas machine for the battery business Webster’s dictionary defines the word Lead acid batteries This helped in acceleration of cars and “scamper” as to run or go hurriedly The first rechargeable lead acid bat- in absorbing the energy while break- and it certainly describes the pace tery was invented by Gaston Planté ing. of activity in the development of in 1859. The cars worked well but required the ideal battery. In creative stud- The chemistry is simple, lead react- complicated electronics to simultane- ies, SCAMPER is an acronym for a ing with sulfuric acid giving power. It ously control battery and super capaci- list of questions in generating new was used initially to electrify US and tor operations. David Lamb at CSIRO ideas. It is a method suggested by Europe and later in automobiles. The (Commonwealth Scientific and Indus- Alex Osborn, a pioneer in creativity advantage was no emission from these trial Research Organization) installed studies, and introduced by Robert F vehicles but had limited range. the capacitor inside the battery and Eberle into this mnemonic: Lead acid battery gives a burst of eliminated the control problems. energy for starting a car but the bat- He converted the anode from pure S = Substitute tery dies if not recharged properly. It lead to 50-50 lead-carbon thus build- C = Combine is not normally used in small mobile ing the super capacitor battery hybrid. A = Adapt applications such as cell phones, lap- CSIRO and Furukawa Battery Com- M = Magnify, modify tops, and toys. pany reported that they can build this P = Put to other uses In the late 1990s, super capacitors “Ultrabattery” at the same cost as a E = Eliminate, minify were combined with lead acid battery. normal lead acid battery. R = Rearrange, reverse The evolution of battery technol- The battery industry is scrambling to come up ogy will be analyzed to show how SCAMPER could have been applied by with technical solutions to meet these needs. inventors. Batteries are used in a gamut SCAMPER can be used to generate new solutions of applications and the requirements are different for different applications. to the problems posed by different applications. The battery industry is scrambling to come up with technical solutions to SCAMPER for lead acid batteries meet these needs. SCAMPER can be used to generate new solutions to the SCAMPER element Examples problems posed by different applica- tions. Put to other use Use in automobiles in addition to electrification There are numerous inventive prob- Combine • Combining super capacitor with lead acid lem solving methods such as TRIZ, battery for use in cars the Theory of Inventive Problem Solv- ing introduced by Genrich Altshuller. • Alloying lead with other elements to improve the The tools, techniques and principles performance of lead have grown globally as a method to aid innovation for technical and physi- Adapt Installation of capacitors inside the batteries cal problems. It is a structured — so- Substitute • Use of nano-porous activated carbon instead of coal called “left brained” —approach to inventiveness that can be used with • Use of carbon foam instead of graphite SCAMPER and other creative prob- • Use of ceramic oxides in place of carbon lem solving techniques. 12 Batteries International Autumn 2009
  2. 2. OPINION Axion Power International invented a new PbC technology. The lead anode Scientists discovered that certain metal alloys have is substituted with nano-porous acti- vated carbon to provide high surface the ability to store atomic hydrogen up to 1,000 area chemistry. times their own volume. This results in higher power deliv- ery, faster recharge, longer life, better discharge capability, less lead usage metically sealed rechargeable battery. hydrogen storage sites thus increasing and hence environmentally improved. Neumann used an elastic diaphragm energy density. Transition metals such This technology is a better option for to shut the current and allow hydrogen as Vanadium, Chromium, and others hybrid cars. and oxygen to react. When the pres- are used. Kurtis Kelley of Caterpillar invented sure is relieved, the diaphragm goes This technology is being developed a method to prevent sulfation of the back to its original position allowing by ECD Ovonics. They say that their negative plate and corrosion of the current flow. technology is used by all NiMH bat- positive plate. Commercial NiCads are now sealed teries. From 1997-2008, over 2 mil- This problem was attributed to vol- to prevent leakage. Resealable ports lion hybrid cars have been made with ume expansion at the metal electrode are designed in the battery for auto- NiMH batteries. and was partly solved by the use of matic venting of gasses. Recent patents describe new methods graphite. Kelley substituted carbon to make nickel hydroxide alloyed with foam for graphite and then deposited Nickel metal hydride metals to suppress oxygen evolution. the active metal. The carbon foam (NiMH) batteries ECD claims that their next generation resists corrosion due to high surface Scientists discovered that certain metal NiMH batteries will be equivalent in area. Firefly Energy is developing this alloys have the ability to store atomic energy and power performance to Li- battery technology for use in cars. hydrogen up to 1000 times their own ion batteries but at half the cost and Atraverda uses a bipolar electrode volume. This technology was trans- half the size. made of electrically conducting tita- ferred to capture hydrogen produced This battery is for automotive appli- nium suboxide ceramic. This mate- at the anode. The hydrogen stored in cations including plug-in hybrid elec- rial exhibits metallic-like electrical the anode can be used reversibly dur- tric vehicles (PHEV). It is also being conductivity and has high corrosion ing recharge of the battery. This is the developed for stationary applications resistance. basis of NiMH batteries. where it will compete with lead acid Their US patent describes a battery The most common example is the batteries. where lead and titanium suboxide are Duracell nickel-metal hydride battery. used. Atraverda claims that its batter- They contain a dilute alkaline potas- Lithium-ion batteries ies will be smaller, lighter, greener and sium hydroxide solution. In the 1980s, rechargeable Lithium-ion more reliable. Use of hydrides eliminates toxic cad- (Li-ion) battery technology evolved Pure lead electrodes have the advan- mium and the memory effect from the from primary lithium batteries. tage of long life and resistance to NiCad battery. Storage density is much In a typical Li-ion battery, the cath- damage by high temperatures and higher than that of NiCads because ode is made of lithium cobalt oxide over-charging; however, the battery hydrogen is a better cathode. NiMH (LiCoO2); the negative electrode is has low power density and is unable endure many charge-discharge cycles made of carbon. While recharging, the to produce large currents. but are not a match for NiCads. lithium metal deposits unevenly on the To overcome this deficiency, lead Ovshinsky used metal alloys with carbon electrode creating spiky struc- alloys have been used. Lead-antimony distorted structure to provide multiple tures (dendrites). These structures can made lead stronger and allowed for taller plate designs. It is resistant to SCAMPER for NiCads damage from repeated cycles and is used in boats, golf carts and fork lifts. SCAMPER element Examples However, it is not suited for stand- Substitute • Substituting Ni and Cd as electrodes for Lead by service due to antimony poisoning of the negative electrode. To achieve • Substituting base for acid as the electrolyte castable lead-antimony electrodes, Adapt • Use of a elastic diaphragm selenium is added. Unlike antimony • Use of hermetically sealed design alloys, calcium alloys perform bet- ter in continuous charge applications. Lead-calcium alloys are not suitable SCAMPER for NiMH battery for cycling services because they age even with repeated shallow cycles. SCAMPER element Examples Nickel cadmium batteries Adapt Use of hydrogen storage technol- Waldemar Jungner of Sweden invented ogy to modify Ni technology the nickel cadmium battery in 1899. Substitute Substituting metal hydride in place of toxic cadmium NiCads are made of a nickel cathode and cadmium anode. NiCads, as with Combine Alloying metals such as V and Cr to cre- lead-acid batteries, have a tendency to ate hydrogen storage sites produce hydrogen and oxygen through electrolysis of water. Modify Modifying the manufacturing process to make alloys Georg Neumann, a German engi- Put to other use Technology use in stationary applications neer, improved the design of the her- Batteries International Autumn 2009 13
  3. 3. OPINION SCAMPER for Li-ion batteries THE POWER FROM SCAMPER element Examples BRAINSTORMING Eliminate Eliminate the use of toxic heavy metals SESSIONS Substitute • Use of graphite in place of coal In brainstorming sessions, SCAMPER can be used to generate new ideas. • Use of organic carbonates in place of Inventors have used SCAMPER organic ethers as electrolytes concepts throughout the develop- • Use of ionic liquids as electrolytes ment of various battery technologies and made significant advances. Adapt Adapting the chemistry of mixed metal Areas that SCAMPER analysis oxide to hold oxygen as oxide points to are nanotechnology with controlled combination of matter on Minify • Use of nano form of mixed metal oxides an atomic and molecular scale. Modify • Use of solid dry polymers and heating them For example, metal alloys such as bimetallic metals with improved Combine • Doping phosphates with energy performance and cycle aluminum, niobium and zirconium time can be rationally designed. Metal shuttling could be facili- • Combining separator and tated through proper choice of electrolyte (soaked polymers) guest-host materials. For example, Put to other use Use of Li-ion battery technology in automobiles inorganic zeolites or organic ligands can be designed to host metals. New green solvents such as the conductivity of these phosphate of Li salt and polyethylene oxide or super- and sub-critical liquids materials by doping them with alu- polyacrylonitrile. This design allows can be utilized as electrolytes. minum, niobium and zirconium and for reduction in size for use in thin manufacturing them in nano form. In film batteries. These Li-poly batteries 2002, he co-founded A123 Systems to have greater life cycle degradation grow and pierce the separators result- manufacture these batteries. than Li-ion batteries. Li-poly batter- ing in rapid chemical reactions leading A common electrolyte for Li-ion ies are being used in PDA’s, iPods and to possible explosion. battery is an organic ether which laptops. Researchers have identified metal can present safety and performance There are two types of Li-poly tech- oxides that can hold oxygen as an issues. nologies. oxide when lithium leaves the lattice Alternate electrolytes such as linear One contains gelled carbonate sol- to the anode. organic carbonates (ethylene carbon- vent. The other contains dry polymer Examples would be Li2MnO3 and ate, dimethyl carbonate, etc.) have to avoid the issues with solvent but LiFePO4. These transition metals can been patented. These carbonates per- has conductivity problems. To over- change valence state easily and keep form over a wide range of tempera- come this deficiency, the dry polymer oxygen as an oxide inherently mak- tures. Ionic liquids have also been used is heated to 60C to increase con- ing the battery system more stable. as electrolytes. ductivity thus limiting its application Even though LiFePO 4 is cheaper Li-ion batteries require the use of potential. and more environmentally friendlier separators, which separate the anode Research is on-going to develop than LiCoO2, it has lower conductiv- and cathode materials while allowing polymers that will conduct at room ity and limited rate of delivery and ions to pass through. Advancements temperature. storage. have led to replacing the separator Yet-Ming Chiang of MIT altered with solid polymer composite made Li sulfur batteries A Li-S battery is composed of a lithium anode and a cathode made of carbon Areas that SCAMPER analysis points to are and sulfur. Li-S and Li-ion batteries nanotechnology with controlled combination of have the same mechanism of Li-ion moving between the two electrodes. matter on an atomic and molecular scale The theoretical capacity of Li-S bat- tery is higher as each sulfur can bind two lithium ions whereas in Li-ion SCAMPER for Li-S batteries battery only 0.5-0.7 lithium ions can SCAMPER element Examples be hosted by the carbon cathode. Although the theoretical capacity of Eliminate Eliminate the use of costly transition metals for sulfur Li-S battery is high, it has the follow- ing issues: Substitute Use polymeric composite membrane as separator Sulfur is insulating and hence only Adapt Adapting nanometer carbon tubes for use at cathode surface sulfur atoms can interact effec- tively with lithium ions. Modify • Increase active surface area by Some lithium sulfur compounds have incorporating sulfur in mesoporous carbon a high solubility in the electrolyte and can precipitate out, blocking charging • Coat the cathode with hydrophilic polyethylene glycol and discharging. 14 Batteries International Autumn 2009
  4. 4. OPINION SCAMPER for lithium air batteries branes to minimize the polymer sepa- SCAMPER element Examples rator breach by the dendrite. Adapt Use chemical reactions that are nor- mally part of fuel cells Lithium air batteries In a Li-air battery, chemical reactions Modify • Use of lithium ion conducting glass film as separator that are normally part of a fuel cell are employed at the cathode. A new • Use of aqueous electrolyte to Li-air battery has been described by dissolve lithium oxide at the cathode the National Institute of Advanced Industrial Science and Technology. AIST used an organic electrolyte and The lithium oxide is soluble in aqueous electrolyte an aqueous electrolyte separated by solid state separator (lithium super-ion and thus the clogging problem is eliminated. conductor glass film or LISICON). The lithium oxide is soluble in aque- ous electrolyte and thus the clogging During use, lithium can grow den- sible to electrons and lithium. The carbon problem is eliminated. Institutions drite structures leading to short tubes effectively decreases the mobility of such as University of St Andrews, IBM circuiting and safety issues. polysulfides and thus increasing conver- Almaden Research Center, Argonne University of Waterloo research- sion to di-lithium sulfide. National Laboratory, AIST, PolyPlus, ers have increased the theoretical BASF has eliminated short-circuiting Quallion, and others are involved in maximum energy density to 84% by by using polymer-composite mem- advancing this technology. n increasing the active surface area of sulfur by incorporating it into mes- oporous carbon. Dr Mark Mack (left) is an innovation expert and the In addition, the surface of the cath- former chief scientist of the ode was coated with hydrophilic poly- petrochemicals giant Lyon- ethylene glycol which decreased the dellBasell Industries, who movement of hydrophobic polysulfide runs from the cathode to the electrolyte. consulting. Dr Rangasamy Another approach is to use well- Pitchai, (right) former R&D packed nanometer carbon tubes as manager at LyondellBasell, is cathodes and filling the spaces between an expert in process, product them with sulfur. and idea development, stage This keeps the sulfur near the conduc- gate and portfolio processes implementation. tive carbon and hence the sulfur is acces- Batteries International Autumn 2009 15