BU-307: How does Electrolyte Work?

Learn more about the catalyst that straddles the electrodes of a battery and makes electricity flow

Electrolyte serves as catalyst to make a battery conductive by promoting the movement of ions from the cathode to the anode on charge and in reverse on discharge. Ions are electrically charged atoms that have lost or gained electrons. The electrolyte of a battery consists of soluble salts, acids or other bases in liquid, gelled and dry formats.  Electrolyte also comes in a polymer, as used in the solid-state battery, solid ceramic and molten salts, as in the sodium-sulfur battery.

Lead Acid

Lead acid uses sulfuric acid. When charging, the acid becomes denser as lead oxide (PbO2) forms on the positive plate, and then turns to almost water when fully discharged. The specific gravity of the sulfuric acid is measured with a hydrometer. (See also BU-903: How to Measure State-of-charge). Lead acid batteries come in flooded and sealed formats also known as valve regulated lead acid (VRLA) or maintenance-free. 

Sulfuric acid is colorless with a slight yellow tint, soluble in water and highly corrosive. Lead acid batteries come with different specific gravities (SG). Deep-cycle batteries use a dense electrolyte with an SG of up to 1.330 to achieve high specific energy, starter batteries contain an average SG of about 1.265 and stationary batteries come with a low SG of roughly 1.225 to moderate corrosion and promote longevity. (See BU-903: How to Measure State-of-charge.).

Sulfuric acid serves a wide range of applications and is also found in drain cleaners and various cleaning agents. It further serves in mineral processing mineral processing, fertilizer manufacturing, oil refining, wastewater processing and chemical synthesis.

CAUTION:  Sulfuric acid can cause serious damage on skin contact and can lead to permanent blindness if splashed in eyes. Swallowing sulfuric acid causes irreversible damage.


Nickel-cadmium (NiCd)

The electrolyte in NiCd is an alkaline electrolyte (potassium hydroxide). Most NiCd batteries are cylindrical in which several layers of positive and negative materials are wound into a jelly-roll. The flooded version of NiCd is used as the ship-battery in commercial aircrafts and in UPS systems operating in hot and cold climates requiring frequent cycling. NiCd is more expensive than lead acid but lasts longer.

Nickel-metal-hydride (NiMH)

NiMH uses the same or similar electrolyte as NiCd, which is usually potassium hydroxide. The NiMH electrodes are unique and consist of nickel, cobalt, manganese, aluminum and rare earth metals, which are also used in Li-ion. NiMH is available in sealed versions only.

Potassium hydroxide is an inorganic compound with the formula KOH, commonly called caustic potash. The electrolyte is colorless and has many industrial applications, such as the ingredient in most soft and liquid soaps. KOH is harmful if indigested.

Lithium-ion (Li-ion)

Li-ion uses liquid, gel or dry polymer electrolyte. The liquid version is a solution of lithium salts with organic solvents similar to ethylene carbonate. Mixing the solutions with diverse carbonates provides higher conductivity and expands the temperature range. Other salts may be added to reduce gassing and improve high temperature cycling.

Li-ion with gelled electrolytes receives many additives to increase conductivity, so does the lithium-polymer battery. The true dry polymer only becomes conductive at elevated temperatures, and this battery is no longer in commercial use. Additives are also administered to achieve longevity and unique characteristics. The recipe is classified and each manufacturer has its own secret sauce. (See also BU-808b: What causes Li-ion to die?

The electrolyte should be stable, but this is not the case with Li-ion. A passivation film forms on the anode that is called solid electrolyte interface (SEI). This layer separates the anode from the cathode but allows ions to pass through much like a separator. In essence, the SEI layer must form to enable the battery to work. The film stabilizes the system and gives the Li-ion a long life but this causes a capacity reduction. Electrolyte oxidation also occurs on the cathode that permanently lowers the capacity. (See also BU-701: How to Prime Batteries)

To prevent the films from becoming too restrictive, additives are mixed with the electrolyte that is consumed during the formation of the SEI layer. It would be difficult, if not impossible, to trace their presence when doing a forensic evaluation. This keeps proprietary additives a trade secret, both their composition and the amount used.  

A well-known additive is vinylene carbonate (VC). This chemical improves the cycle life of Li-ion, especially at higher temperatures, and keeps the internal resistance low with use and age. VC also maintains a stable SEI film on the anode with no adverse side effects of the electrolyte oxidation on the cathode (Aurbach et al). It is said that academic and research communities are lagging behind cell manufacturers in knowledge and choice of additives, hence the great secret. (See also “Additives and the Effects on Coulombinc Efficiency” as part of  BU-808b: What causes Li-ion to die?

Last Updated 2016-05-04

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On December 28, 2015 at 1:33pm
Thomas wrote:

What confuses me is, why doesn’t the anode and cathode short out through the electrolyte if it conducts electricity? Am I missing something here? Is it only able to conduct when the anode and cathode are connected externally?

On February 1, 2016 at 4:29am
Simon Cowell wrote:

Fuck bitches and get bare money fam $$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$.

On February 10, 2016 at 7:25pm
Michael Bates wrote:

Thomas, the electrolyte conducts ions, not electrons. The flow of electrons through the external circuit must be balanced by the flow of ions through the electrolyte (similar to a “salt-bridge” in a typical Gen.Chem. Cu/Zn galvanic cell demo). Therefore, if the ionic conductivity of the electrolyte is too low, that becomes the “bottleneck” limiting cell discharge rates.
For the author(s), it would be very helpful to expand this section somewhat to discuss the LiB solvent compositions. For instance, what effect does the relative composition of EC, DMC, DEC or EMC have on the battery performance?
Thanks for developing this outstanding web resource!

On March 7, 2016 at 8:07pm
Santa Claus wrote:

So basically the electrolyte is the 2 other parts combined? Very helpful

On May 15, 2016 at 9:49pm
Jason wrote:

So the functions of electrolyte are enabling the flow of mobile ions and balancing the charge of the chemical cell. Am I right?

On May 15, 2016 at 10:07pm
Jason wrote:

And I would like to ask why can’t the two electrodes be totally submerged into the electrolyte in a chemical cell?

On October 8, 2016 at 1:43pm
Clair Smyers wrote:

I do not understand the functions fully but what Thomas wrote was answered in the next comment. I did indeed remember that the internal conduction in the cell is ionic. The external conduction is electrons. It’s been a while since I have studied this but it’s worth revisiting. Thank you for what you wrote Micheal.

On January 10, 2017 at 3:27am
mir mehraj wrote:

Can SEI formation be prevented /restricted or completely avoided in Lithium batteries?

On February 16, 2017 at 12:02pm
Mohsin wrote:

How can we prepare Red lead (lead Dioxide) from lead at home in easy way smile