History of Batteries

Baghdad Battery

Discovered in the 1930s, the urn dated back to sometime between 250 B.C. and A.D. 250. Obviously this was many, many years before modern batteries were invented in the 19th century. The artifact contained a copper pipe with an iron rod in its center; it is possible that these were the electrodes of a battery.  Inside the urn was the residue of an acidic liquid that was possibly the electrolyte and it was capped with an asphalt cork with the iron rod protruding through.  They are believed to have been used by the Parthian civilization that occupied the region during this time period as a source of electricity to plate gold onto silver.  Electroplating requires a small electric current to put a thin layer of one metal , for example gold, onto the surface of another metal, possibly silver.  

Volta Pile

The voltaic pile was invented in 1800 by Count Alessandro Volta.  It was Galvani that had earlier discovered that he could make a frog’s legs twitch by placing two dissimilar metal probes against its tissue.  Galvani regarded their activation as being generated by an electrical fluid that is carried to the muscles by the nerves and he termed it “animal electricity”.  Volta disagreed with Galvani and believed that the frog's tissue served as both a conductor of electricity (what we would now call an electrolyte) and the twitching as a detection of electricity.  

In 1800, as the result of this professional disagreement over the galvanic response advocated by Galvani, Volta invented the voltaic pile.  The original voltaic pile consisted of a pile of zinc and silver discs and between alternating discs were cardboard pieces soaked in saltwater. A wire connecting the bottom zinc disc to the top silver disc produced electric current. 

The battery made by Volta is credited as the first electrochemical cell.For this, and his other work with electricity, we commemorate his name in the measurement of electric potential called thevolt.

Leclanché Battery

In 1866, Georges Leclanché invented a battery that consisted of a zinc anode and a cathode of manganese dioxide wrapped in a porous material.  The electrodes were immersed in a jar of ammonium chloride solution. Similar to its use in lithium-ion cells today, a small amount of carbon was mixed into the manganese dioxide to improve conductivity and increase electrolyte absorption.  The Leclanché cell had a voltage of 1.4 volts. This cell was well received and by 1868 twenty thousand Leclanché cells were being used in telegraph systems. The original Leclanché cells were easily breakable.  Eventually the design was modified into what are known as "dry cells" which became widely used in the first flashlights (1909) and in battery-powered radios in the 1920’s.

Planté Battery

In 1859 Planté’s experiments resulted in the lead-acid battery;the first battery that could be recharged by passing a reverse current through it.  Planté's first model consisted of two lead sheets separated by rubber strips and rolled into a spiral.  One year later he presented a  multi-cell battery compromised of nine of the lead cells housed in a protective box with the terminals connected in parallel. His battery could deliver remarkably large currents.

Although his battery could deliver large currents, one disadvantage of Planté battery is that it could only supply voltage for a short period of time as the cathode had only a small amount of active lead oxide material available during the discharge reaction. This issue was solved by Camille Faure in 1881; where Faure used a set of electrodes consisting of lead paste spread thinly on the electrode surface, providing better plate efficiency with more lead oxide resulting in a longer discharge.

Edison Battery 1905 Nickel-iron Cell

Edison believed that lead-acid batteries were both too heavy and that it was not a good idea to use a corrosive electrolyte.  After much experimentation, which is Edison’s trademark, he developed a working alkaline battery. The Edison cellused an iron anode, nickel oxide cathode, and KOH electrolyte. This cell was extremely simple and rugged in design; and can still be found in some industrial applications today, but it was never able to replace the lead-acid cell as Edison had hoped.  

Primary and Rechargeable Cylindrical Cells

From left to right:

Varta and English Eveready No.8 batteries (2xBF unit cell) zinc-carbon cells

Pair of BF zinc-carbon cells (Eveready 927)

Zinc-carbon “B” cell (taken from a dead Eveready 703) (A “D” cell is behind the “B” cell for height comparison.)

Protected “18500” lithium cell

NiCd “A” cell

Alkaline “AA” cell

In 1905 Ever Ready was selling flashlights and batteries using zinc-carbon cells; later shortening the name to Eveready in 1917.   The zinc-carbon system used ammonium chloride or zinc chloride solutions for the electrodes.  In the 1950’s Urry, working at Union Carbide’s Eveready Battery division invented the alkaline version of the zinc-carbon cell.   Alkaline cells have 3-5 times the capacity of an equivalent sized zinc-carbon cell and are therefore the primary cell of choice today.

Nickel Cadmium and Nickel Metal Hydride

Waldmar Jungner invented the nickel-cadmium battery in 1899 but due to the use of expensive materials they were not fully commercialized for many years.  Larger ventilated wet cell NiCd batteries are still used today in aircraft, rail, mass transit, emergency lighting, standby power, and uninterruptible power supplies and other applications; when larger capacities and high rate discharges are required.  Sealed nickel-cadmium batteries were developed in the 1940’s.  Rather than venting, the internal gases generated during charge were recombined. These advances led to the modern sealed nickel-cadmium battery; although environmental issues with cadmium have led to restrictions and some bans on the use of these batteries in consumer applications.

The nickel metal hydride battery was invented in 1967 but required over 20 years of development into the 1990’s before it began to take serious market share from nickel cadmium batteries due to a large improvement in energy density (and environmental issues).Both the nickel-cadmium and nickel-metal hydride cells usenickel oxyhydroxide (NiOOH) for their positive electrodes.In a nickel-metal hydride cell the negative cadmium electrode is replaced with a hydrogen-absorbing alloy.

Lithium-ion Cylindrical and Prismatic Cells and Batteries

Lithium-ion batteries are a family of rechargeable battery types in which lithium ions move from the negative electrode to the positive electrode during discharge and back when charging.  Compared to lithium metal anode batteries, lithium-ion batteries use an intercalated lithium compound as the anode, compared to metallic lithium. Anode materials were originally carbons and graphites but now include high energy silicon and high power lithium titanate. There are many different cathode intercalation active materials including lithium cobalt oxide, lithium manganese spinel, lithium nickel-manganese-cobalt oxide, lithium nickel-cobalt-aluminum oxide and lithium iron phosphate.

 Following many years of developments in lithium metal and intercalation materials by scientists including Whittingham, Goodenough, Yoshino, Besenhard and Yakima; lithium-ion batteries were first commercialized by Sony in 1991 and Asahi-Toshiba in 1992.  (In 2019, Whittingham, Goodenough and Yoshino were awarded the Nobel Prize in Chemistry).  Moli Energy, a Canadian company, was the first to commercialize lithium-ion batteries in North America in 1994.  (I was fortunate enough to be part of the product development team at Moli Energy).

The most standard cylindrical cell type is the 18650 cell.  This cell measures 18mm in diameter and 65 mm in length.  The 18650 is 1.5mm larger in diameter than a 4/3A cell, one of the most common sizes for nickel metal hydride (NiMH) cells in the 1990’s. Although NiMH cells were only 1.2V vs. 3.6V for lithium-ion, a 3x hit in voltage.  Cells and batteries that have different chemistries are compared to using energy and not capacity.  Energy is the product of the cell capacity and voltage.  NiMH cells in the 1990’s had higher energy density than lithium-ion in the 4.3A format, a cell design that measures 16.5mm in diameter x 65mm in length.  To compete with higher total energy, Sony, the first to commercialize lithium-ion increased the diameter of the lithium-ion cell to 18mm, which then surpassed the 4/3A NiMH cell.  This was important for Sony to break into the portable computer market albeit a sleight-of-hand.

 Other applications including mobile phones however needed thinner cells due to their form factor.The prismatic cell was created, the first being 8mm in thickness.A common size for this metal can was 34mm wide x 48mm long x 8mm thick.The largest customer for the first small prismatic cells was Motorola for their StarTac phone.Technology evolved quickly and Motorola shrunk their battery requirements to 6mm so that the battery did not protrude from the mobile phone.Prismatic cells 6mm in thickness were designed and manufactured.However, when Motorola requested cell manufacturers to decrease their thickness to 5mm, a new cell design was needed.The thickness of the metal can wall became an increasingly higher percentage (>10%) of the total can volume dramatically lowering the energy available.

Lithium-ion Pouch Cells

The solution to the mobile phone’s requirement for thinner and thinner cells was the pouch cell design where a polymer-aluminum laminate, similar to that used in some brands of potato chips, replaced the metal can. This flexible laminate material was 1/3 the thickness of the prismatic cell’s metal can. The other major advantage of the pouch cell was the ease of bringing new cell sizes into production. Where an automated prismatic cell line took many months to convert to a different cell size, new pouch cells could be designed in only days to weeks. This is also about the time cells began to be manufactured in China. Low manual labor rates in China allowed for cost-effective hand assembly of consumer lithium-ion pouch cells. Since then most companies use semi-or fully automated lines, the latter for high volume accounts. The lithium-ion pouch cell is now a very important cell type being used in mobile phones and tablets. Pouch cells have even enabled portable computers to be designed ultra-thin by replacing the 18mm diameter cylindrical cells commonly used.