History of the lithium-ion battery

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This is a history of the lithium-ion battery.

Before lithium-ion: 1960-1975

• 1960s: Much of the basic research that led to the development of the intercalation compounds that form the core of lithium-ion batteries was carried out in the 1960s by Robert Huggins and Carl Wagner, who studied the movement of ions in solids.^[1]
• 1970s: Reversible
  TU Munich. Besenhard proposed its application in lithium cells.^[7][8]
  What was missing in Besenhard's batteries is an electrolyte, that would prevent solvent co-intercalation into graphite, electrolyte decomposition and corrosion of current collectors. Thus, his batteries had very short cycle lives.
• 1970s: Reversible intercalation of lithium ions into layered cathode materials. British chemist M. Stanley Whittingham, then a researcher at ExxonMobil, first reported a charge-discharge cycling with a lithium metal battery (a precursor to modern lithium-ion batteries) in the 1970s.^[4] Drawing on previous research from his time at Stanford University,^[9] he used a layered titanium(IV) sulfide as cathode and lithium metal as anode.^[4][10] However, this setup proved impractical. Titanium disulfide was expensive (~$1,000 per kilogram in the 1970s) and difficult to work with, since it has to be synthesized under completely oxygen and moisture-free conditions. When exposed to air, it reacts to form hydrogen sulfide compounds, which have an unpleasant odour and are toxic to humans and most animals. For this, and other reasons, Exxon discontinued development of Whittingham's lithium-titanium disulfide battery.^[1]

Batteries with metallic lithium electrodes presented safety issues, most importantly the formation of lithium

• 1973:
  lithium metal
  and was not rechargeable.

Precommercial development: 1976-1990

• 1976:
  Exxon demonstrated what can be considered the first rechargeable "lithium-ion battery", although not a single component in this design was used in commercial lithium-ion batteries later.^[13] Whittingham's cell was assembled in a charged state using lithium aluminum alloy as the negode, LiBPh4 (lithium tetraphenylborate) in dioxolane as the electrolyte and TiS2 as the posode. The battery useful cycle life was no more than 50 cycles. This design was based on Whittigham's earlier Li-metal batteries.^[14]
• 1977: Samar Basu et al. demonstrated irreversible intercalation of lithium in graphite at the University of Pennsylvania.^[15][16] This led to the development of a workable lithium intercalated graphite electrode at Bell Labs in 1984 (LiC
  ₆)^[17] to provide an alternative to the lithium metal electrode battery. However it was only a molten salt cell battery rather than a lithium ion battery.
• 1978: Michel Armand introduced the term and a concept of a rocking-chair battery,^[18] where the same type of ion is de/intercalated into both positive and negative electrode during dis/charge. In the rocking-chair design solution-phase species do not appear in the reaction stoichiometry, which allows for minizing the amount of solvent in the battery, reduces the battery weight and cost.
• 1979: Working in separate groups, Ned A. Godshall et al.,
  Tokyo University), demonstrated limited discharge-charge cycling of a 4 V cell made with lithium cobalt dioxide (LiCoO
  ₂) as the positive electrode and lithium metal as the negative electrode.^[22][23] This innovation provided the positive electrode material, which eventually became a component in the first commercial rechargeable lithium-ion battery. LiCoO
  ₂ is a stable positive electrode material which acts as a donor of lithium ions, which means that it can be used with a negative electrode material other than lithium metal.^[24] By enabling the use of stable and easy-to-handle negative electrode materials, LiCoO
  ₂ enabled novel rechargeable battery systems. Godshall et al. further identified the similar value of ternary compound lithium-transition metal-oxides such as the spinel LiMn₂O₄, Li₂MnO₃, LiMnO₂, LiFeO₂, LiFe₅O₈, and LiFe₅O₄ (and later lithium-copper-oxide and lithium-nickel-oxide cathode materials in 1985)^[25] Godshall et al. patent U.S. patent 4,340,652^[26]
  for the use of LiCoO₂ as cathodes in lithium batteries was based on Godshall's Stanford University Ph.D. dissertation and 1979 publications.
• 1980: M.Lazzari and
  tungsten dioxide as the anode, titanium disulfide as the cathode and lithium perchlorate in propylene carbonate as the electrolyte.^[27]
• 1980's: The negative electrode has its origins in PAS (polyacenic /
  conductive polymers by Professor Hideki Shirakawa and his group, and it could also be seen as having started from the polyacetylene lithium ion battery developed by Alan MacDiarmid and Alan J. Heeger et al.^[32]
• 1980: following Samar Basu's report of Li+ intercalation into graphite at high temperature (see 1977 above), Rachid Yazami demonstrated the reversible electrochemical intercalation of lithium in graphite at room temperature.^{[33][34][35][36]} The organic battery solvents, known at the time, decompose during charging with a graphite negative electrode. For this reason, Yazami used a solid electrolyte to demonstrate that lithium could be reversibly intercalated into graphite via an electrochemical mechanism at room temperature.
• 1983: Michael M. Thackeray, Peter Bruce, William David, and John B. Goodenough developed manganese spinel, Mn₂O₄, as a charged cathode material for lithium-ion batteries. It has two flat plateaus on discharge with lithium one at 4V, stoichiometry LiMn₂O₄, and one at 3V with a final stoichiometry of Li₂Mn₂O₄.^[37]
• 1985:
  polyvinylidene difluoride
  as the binder.
• 1986 : Around the same time as Akira Yoshino, Auborn and Barberio at Bell Laboratory independently demonstrated another true rocking-chair battery assembled in the fully discharged state. Their 1.8 V lithium-ion battery comprised LiCoO2 as the posode, 1M LiPF6 in propylene carbonate as the electrolyte and MoO2 as the negode.^[39]
• 1986 : Asahi researchers, led by Akira Yoshino, demonstrated rechargeable battery with lithium tetrafluoroborate (LiBF4) dissolved in a mixture of PC, gamma-butyrolactone (γBL) and ethylene carbonate (EC), as the electrolyte. The fluorinated anion turned out to be effective in passivating the Al current collector and compatible with the solvents, while ethylene carbonate (which is solid at room temperature and is mixed with other solvents to make a liquid) provided th necessary solid electrolyte interphase on the anode, thus publicly disclosing the final piece of the puzzle leading to the modern lithium-ion battery.^[40] This design was practically identical (except for LiBF4 being replaced with LiPF6, which is less reactive with the solvent(s)) to the one used in commercial lithium-ion batteries today.
• 1987-1989:
  polyanions, e.g., sulfates, produce higher voltages than oxides due to the inductive effect of the polyanion. This polyanion class contains materials such as lithium iron phosphate.^[44]
• 1989:The recall of Moli Energy cells, comprising lithium metal, abruptly changed researchers’ perception in favor of heavier but safer dual-intercalation (i.e. lithium-ion rather than lithium-metal) batteries.[40]
• 1989-10-11:
  LiPF6
  .
• 1990:
  lithium-ion batteries, eventually discovering the magic ethylene carbonate solvent, which resulted in almost doubling (to 155 Wh/kg) the specific energy of cells with soft carbon anodes.^[46]
• 1990-12-10:
  LiPF6 as the electrolyte.^[47]
• 1990: The English term "
  lithium metal batteries appeared for the first time in a publication.^[46] It was used by Sony employees.^[48]

In 2017 (2 years before the 2019 Nobel Prize in Chemistry was awarded) George Blomgren offered some speculations on why Akira Yoshino's group produced a commercially viable lithium-ion battery before Jeff Dahn's group:^[49]

• The Dahn group tested the carbonaceous positive electrode against lithium instead of a metal oxide. Therefore, they did not observe the severe corrosion of an aluminum positive
  LiPF6
  , which was commonly used for primary lithium metal batteries in Japan.
• Yoshino et al. also studied various binders including the ultimate winner-
  ethylene propylene diene monomer
  (EPDM), which turned out to be not durable enough for commercial LIBs.

Commercialization in portable applications: 1991-2007

The performance and capacity of lithium-ion batteries increased as development progressed.

• 1991:
  magnetic tapes.^[52]
• 1994: iconectiv First commercialization of Li polymer by Bellcore.^[53]
• 1994: The first aqueous Li-ion “rocking chair” chemistry was demonstrated by Dahn et al. It had a VO2 anode and LiMn2O4 cathode in a 5 M LiNO3 electrolyte with 1 mM LiOH.^[54]
• 1996: Goodenough, Akshaya Padhi and coworkers proposed lithium iron phosphate (LiFePO
  ₄) and other phospho-olivines (lithium metal phosphates with the same structure as mineral olivine) as positive electrode materials.^[55][56]
• 1996: Sony and Nissan announced a partnership to develop a lithium-ion battery powered car FEV II with a 124 mile driving range.^[57]
• 1998: C. S. Johnson, J. T. Vaughey, M. M. Thackeray, T. E. Bofinger, and S. A. Hackney report the discovery of the high capacity high voltage lithium-rich
  NMC cathode materials.^[58]
• 2001: Arumugam Manthiram and co-workers discovered that the capacity limitations of layered oxide cathodes is a result of chemical instability that can be understood based on the relative positions of the metal 3d band relative to the top of the oxygen 2p band.^[59][60][61] This discovery has had significant implications for the practically accessible compositional space of lithium ion battery layered oxide cathodes, as well as their stability from a safety perspective.
• 2001: Christopher Johnson, Michael Thackeray, Khalil Amine, and Jaekook Kim file a patent
  lithium nickel manganese cobalt oxide
  (NMC) lithium rich cathodes based on a domain structure.
• 2001: Zhonghua Lu and Jeff Dahn file a patent^[64] for the NMC class of positive electrode materials, which offers safety and energy density improvements over the widely used lithium cobalt oxide.
• 2002:
  LiFePO4 material's conductivity by doping it^[65] with aluminium, niobium and zirconium. The exact mechanism causing the increase became the subject of widespread debate.^[66]
• 2004:
  John Goodenough.^[66]
• 2004: The number of non-patent publications about lithium-ion batteries from
  USA. Japan was the third leading country till 2011, when it was surpassed by South Korea
  .
• 2005: Y Song, PY Zavalij, and M. Stanley Whittingham report a new two-electron vanadium phosphate cathode material with high energy density^[67][68]

Commercialization in automotive applications: 2008-today

• 2008: The launch of Tesla Roadster- the first highway legal, serial production, all-electric car to use lithium-ion battery cells, and the first production all-electric car to travel more than 244 miles (393 km) per charge- ushered a new era in the history of Li-ion batteries, which is signified as inflection points in the plots "The log number of publications about electrochemical powersources by year" and "The number of non-patent publications about lithium-ion batteries" shown on this page.
• 2011:
  Lithium nickel manganese cobalt oxide (NMC) cathodes, developed at Argonne National Laboratory, are manufactured commercially by BASF in Ohio.^[69]
• 2011: Lithium-ion batteries accounted for 66% of all portable secondary (i.e., rechargeable) battery sales in Japan.[70]
• 2012: John Goodenough, Rachid Yazami and Akira Yoshino received the 2012 IEEE Medal for Environmental and Safety Technologies for developing the lithium ion battery.^[36]
• 2014:
  John Goodenough, Yoshio Nishi, Rachid Yazami and Akira Yoshino were awarded the Charles Stark Draper Prize of the National Academy of Engineering for their pioneering efforts in the field.^[71]
• 2014: Commercial batteries from Amprius Corp. reached 650
  Wh/L (a 20% increase), using a silicon anode and were delivered to customers.^[72]
• 2016: Koichi Mizushima and Akira Yoshino received the NIMS Award from the National Institute for Materials Science, for Mizushima's discovery of the LiCoO₂ cathode material for the lithium-ion battery and Yoshino's development of the lithium-ion battery.^[73]
• 2016: Z. Qi, and Gary Koenig reported a scalable method to produce sub-micrometer sized LiCoO
  ₂ using a template-based approach.^[74]
• 2019: The
  Stanley Whittingham and Akira Yoshino "for the development of lithium ion batteries".^[75]
• 2022: Battery startup SPARKZ announced plans to convert a glass plant in Bridgeport, WV to produce zero-cobalt lithium batteries.^[76]

Market

Industry produced about 660 million cylindrical lithium-ion cells in 2012; the

Prices of lithium-ion batteries have fallen over time. Overall, between 1991 and 2018, prices for all types of lithium-ion cells (in dollars per kWh) fell approximately 97%.[77] Over the same time period, energy density more than tripled.^[77] Efforts to increase energy density contributed significantly to cost reduction.^[81]

In 2015, cost estimates ranged from $300–500/kWh^[