UNIT – IV

BATTERIES FOR AUTOMOTIVES FUTURE PROSPECTS

LITHIUM ION BATTERY RECYCLING

BY
Dr. S. SIVA ILANGO
ASSISTANT PROFESSOR
DEPARTMENT OF CHEMISTRY
THIAGARAJAR COLLEGE OF ENGINEERING
MADURAI 15
RECYCLING TECHNOLOGIES OF THE SPENT
LITHIUM ION BATTERIES

The Chemical composition of a typical lithium-ion secondary

rechargeable battery is presented the Table
The components in Lithium ion battery
The recycling technologies extract the valuable materials from the
spent lithium ion batteries through the difference properties of
different components and the recycling should be understood from
the context of the value of the components.
The cost breakdown of the components presented in figure below
 From the figure above, it could be observed that the most cost
consuming components are cathode materials, Lithium salt in
electrolyte and Anode materials.

Conclusively, there are basically three methods for battery-recycling:

separation of components through unity operations of mining
treatment, pyrometallurgy and hydrometallurgy.

However, in order to descript the three methods, this paper divided

the whole process into three parts:

(1) pretreatment which includes discharge, crush, screening with the

purpose of getting the anode materials (LiCoO2);
(2) extraction of valuable metals (recovery of LiCoO2 directly) that
means detaching valuable materials roughly;
(3) further process which purifies the valuable metals of the step 2.
The process is shown in Figure below
DESCRIPTION OF EXTRACTION PROCESSES
PRE TREATMENT
Mechanical crushing:
The method means to realize liberation of each component by
crushing which can break the structure of the spent LIBs.

Heat-Treatment:
The heat-treatment mainly eliminates the organic binder between
aluminum foil and cathode material, then separate them by screen
separation.
Specific details are as follows:
Firstly, the spent lithium-ion batteries are calcinated at 100~500℃
for 2 h; then the materials are crushed by a special crusher; finally
the broken products are reheated at 300~500℃ for 1h. The final
products are mixture of cathode material and carbon.
Dissolution:
The dissolution means to wash the cathode material off the
aluminum foil, which is on the basis of the theory of ― similarity and
intermiscibility. Usually, the cathode and anode strips are immersed
in 2,5-dimethylpyrrolidine at about 100℃ for 1 hour for the de-
lamination of Alumninium substrate and Copper substrate from
Cathode and Anode, respectively.

Ultrasonic Washing:
Ultrasonic washing is an effective process for separate the
electrode materials from plastic and iron scrap by using ultrasonic
washing. Ultrasonic washing can produce impact force caused by
small bubbles explosion which would separate cathode material off
the aluminum foil.
Firstly, spent LIBs are crushed and sieved (the screen mesh is
12mm), then the undersized products are ultrasonic washed and
sieved again, and the undersized products are the final products.
EXTRACTION OF VALUABLE METALS
The main components of the materials after pretreatment are
carbon black and LiCoO2. To realize the resource reuse of the spent
LIBs, these materials need to be purified further.
There are two methods in this process:
 Chemical leaching,
 Mechanochemical process,
 Biotechnology.
CHEMICAL LEACHING
Chemical leaching , which leaches the valuable metals from materials
by acid or alkaline in order to transfer the metals to the aqueous liquor, is
widely used in this process.
The leaching of LiCoO2 from spent LIBs is usually carried out by
using inorganic acids such as sulphuric acid, hydrochloride acid and nitric
acid.
The Co and Li are easily leached from spent LIBs using quite dilute
acid solutions but reducing agents like hydrogen peroxide (H2O2) are
required, otherwise more concentrated acid solutions are necessary to
obtain comparative dissolutions
The leaching reactions of LiCoO2 of LIBs in H2SO4 and HCl are as
follows
MECHANOCHEMICAL PROCESS
Mechanochemical process was investigated to extract cobalt and
lithium from spent LIBs. In this process, polyvinyl chloride (PVC)
and the material after pretreatment are mixed and placed in a ball
mill, then the mixture is grinded in air.
Cobalt and lithium would form respective chloride which can be
soluble in water. After filtration, cobalt and lithium can be separated
from other insolubles.

BIOTECHNOLOGY
In this method, Co(Ⅲ) is reduced to Co(Ⅱ) by Fe(Ⅱ) generated
by thiobacillus ferrous oxide and thiobacillus thio oxidans.
Biotechnology has the advantages of mild conditions and
environment friendly.
However, biotechnology has been used in laboratory research at
present because of strict conditions until now.