DESC:FORM – 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
10 COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
LEAD ACID BATTERY PASTE
Applicant:
Bharat Forge Limited,
15 Mundhwa, Pune 411036,
Maharashtra, India
THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES
THE INVENTION AND THE MANNER IN WHICH IT IS TO BE
PERFORMED.
20
2
5 FIELD OF INVENTION
The present invention relates to a battery. More particularly, the present invention relates to a lead
acid battery. Still more particularly, the present invention relates to positive and negative active
materials inside a lead acid battery.
BACKGROUND
10 Lead acid batteries have been known since last 150 or more years and they still continue to
remain the technology of choice for automotive SLI (Starting, Lighting and Ignition)
applications and a host of other applications which include cell phone towers, highavailability
settings like hospitals, and stand-alone power systems.Lead acid batteries are
low in cost and they are still preferred in many applications because they are robust,
15 tolerant to abuse and above all tried and tested.
Several attempts have been made to improve energy density of the lead acid batteries.
Despite of many developments, there still exists a need for batteries that are charged
quickly and which possess very high energy density.
OBJECTS
20 Accordingly, it is an object of the present invention to provide lead acid batteries with high
electrical performance with improved version of life performance for high end industrial
application.
SUMMARY:
In one aspect of the present invention, there is provided a method of improving the
25 performance of a lead acid battery. The method comprises the following steps :
a. preparing a first and a second dispersion of nano-particulate carbenous materials
comprising one dimensional carbon nanotubes and two dimensional graphene
respectively;
b. preparing a first and a second colloidal solutions of nano-particulate noble metals
30 comprising positively charged and negatively charged noble metal particles
respectively;
c. preparing a first and a second carbenous nano-composites by adding the first and
second dispersions of nano-particulate carbenous material to the first and second
colloidal solutions of nano-particulate noble metals;
35 d. heating the first and second nano-composites in an hot air oven at a temperature
ranging from 80 to 1100C for a period ranging from 7 hours to 12 hours. to obtain
the first and second nano-composites in powder form;
e. doping positive active material and negative active material with the first and
second nano-composites in poweder form respectively; and
3
f. loading the doped postive and negative active materials in the 5 battery grid to obtain
a battery with improved performance.
In another aspect of the present invention, there is provided, a lead acid battery with
improved performance prepared by the method of the present invention. The lead acid
battery of the present invention comprises positive active materials (PAM) andnegative
10 active materials(NAM) of the battery doped with nano-composites in an amount
ranging from 0.001 to 0.1% wt.
BRIEF DESCRIPTION OF DRAWINGS
The accompanying drawings are included to provide a further understanding of the present
disclosure, and are incorporated in and constitute a part of this specification. The drawings
15 illustrate various embodiments of the present invention and, together with the description,
serve to explain the principles of the present disclosure.
Figure 1 shows schematic representation of impregnation of carbonaceous nanomatrix 1D
carbon nanotubes with 2D Graphene called carbonaneous nanomatrix with noble metal
nanoparticles.
20 Figure 2 A shows the SEM Images of the Ag – Silver Noble Metal 2B- CNT Ag-Silver
Noble metal, 2C TEM images of Ag-Noble Metal & 2D TEM images of CNT decorated
with Ag Noble Metal.
Figure 3 A shows the SEM Images of the Au – Gold Noble Metal 2B- Graphene Au-Gold
Noble metal , 2C TEM images of Au-Noble Metal & 2D TEM images of Graphene
25 decorated with Au Noble Metal.
Figure 4 A shows the SEM Images of the Control Positive paste 4B- Nano
composite ( CNT- Ag Silver noble metal (+ve) , 4C SEM images of Control Negative
paste 4D SEM images of Nano composite ( Graphene - Au gold Noble Metal +ve
paste).
30 Figure 5
Figure 6
DESCRIPTION
Definitions:
The terms and phrases as indicated in quotation marks (“ ”) in this section are intended to
35 have the meaning ascribed to them in this ‘Definitions’ section applied to them throughout
this document, including in the claims, unless clearly indicated otherwise in context.
In accordance with one aspect of the present invention, there is provided a method for
improving the performance of a lead acid battery.
The method of the present invention comprises following steps:
4
a. preparing two separate dispersions of nano-particulate 5 carbonaceous materials
comprising one dimensional carbon nanotubes and two dimensional graphene
respectively;
b. preparing two separate colloidal solutions of nano-particulate noble metals
comprising positively charged and negatively charged noble metal particles
10 respectively;
c. preparing two different carbonaceous nano-composites by adding the dispersions of
carbon nano tubes and two dimensional graphene nano-particles to colloidal
solutions of nano-particulate silver and palladium noble metals and gold and
platinum metals resepctively;
15 d. heating the nano-composites, namely carnon nanotubes-Silver-Palladium( CNTAg/
Pd) and graphene-gold-platinum (graphene-Au/Pt) Ag in an hot air oven at a
temperature ranging from 80 to 1100C for a period ranging from 7 hours to 12
hours to obtain the respective nano-composites in powder form;
e. doping positive active material and negative active material with ( CNT-Ag/Pd) and
20 graphene-gold-platinum (graphene-Au/Pt) in powder form respectively in an
amount ranging from in an amount ranging from 0.001 to 0.1% w/w
f. loading the doped postive and negative active materials in the battery grid to obtain
a battery with improved performance.
The method of the present invention employs positively charged nanno-particulate noble
25 metals which include silver and palladium. The negatively charged nanno-particulate noble
metals employed in the method include gold and platinum. Typically, the particle size of
the noble metal particles ranges from 10 nm to 50nm.
Typically, the method of preparaing a colloidal dispersion of nano-particulate noble metals.
comprises the following steps:
30 ? providing an aqueous precursor solution of noble metals with a molar
concentration ranging from 10-2M to 10-4M in ultra-purified distilled water;
? preparing an extract of lemon grass by boiling lemon grass in distilled water;
? heating the aqueous precursor solution at a temperature ranging from 50 to700 C
under continuous stirring and adding the extract of lemon grass to the boiling
35 precursor solution under stirring in an amount ranging between 5 to 10% and
? verifying the formation of colloidal dispersion by observing the color change.
The noble metal nanoparticles are synthesized through biochemical reduction method by
using the respective noble nanoparticle precursors like chloroauric acid, silver nitrate,
hexachloroplatinic acid and palladium chloride, a biochemical reducing agent which also
40 acts as a capping agent and extract from the lemon grass.
5
The extract is prepared as follows: the 100gm of lemon grass is 5 washed with distilled water
and boiled with 200ml of distilled water till the volume reached to 50ml of concentrated
solution followed by 5ml of the extract is taken and added to the 10-3M concentration of
metal salt solution, after 15mins the color of the solution changes to brown ( Pt/Pd), Yellow
( Ag) and Purple( Au), which is further confirmed by UV-Visible spectroscopy, with a ?
10 max-420nm/540nm.
The reaction rate in this is typically controlled by the reaction conditions. The different
reaction parameters (e.g. reactant concentration, addition rate for reducing agent) are
optimized to obtain the noble nanoparticles. The method of the present invention produces
the colloidal dispersion of noble nanoparticles in the range of 10-50 nm in size and
15 different shapes (spherical, triangular), as characterized by Transmission Electron
Microscopy and Particle Size Analyzer. The biochemical reducing agent acts as a capping
agent and acts a redox reagent.
Typically, the carbonaceous material used for preparing dispersions are one dimensional
carbon nano tubes and two dimensional graphene particles. One-dimensional (1D)
20 nanostructures, such as carbon nano-tubes, are poised to become important building blocks
for molecule-based, electrical circuits. These materials not only offer the potential to serve
as interconnects between active molecular elements in a device but also have the ability to
function as the device element itself. Carbon nano-tubes (CNTs) are allotropes of carbon
with a cylindrical nanostructure. CNTs enhance the electrochemical properties of the
25 electrolyte material PAM by first acting as a conductive support ideal for electron
transportation and secondly stabilize the electrode structure with a good electric contact.
Particle size of the one dimensional carbon nano-tubes typically ranges from 30 to 50nm.
Graphene, a sheet of carbon atoms bound together in a honeycomb lattice pattern, is a
potent conductor of electrical and thermal energy, extremely lightweight chemically inert,
30 and flexible with a large surface area. In the field of batteries, conventional battery
electrode materials (and prospective ones) are significantly improved when enhanced with
graphene. It extends the battery’s life-time, which is negatively linked to the amount of
carbon that is coated on the material or added to electrodes to achieve conductivity.
Graphene adds conductivity without requiring the amounts of carbon that are used in
35 conventional batteries. The particle size of the two dimensional graphene particles
employed in the method of the present invention ranges from 3 to 5 nm. Further, the two
dimessional graphene particles are characterized by average lateral size varying from about
5 to about 10 microns and surface area ranging from about 250 to 300 m2/g.
Typically, the method step of preparing the dispersions of nano-particulate carbonaceous
40 materials comprises :
6
dispersing a nano-particulate carbonaceous material selected 5 from the group consisting of
one dimensional carbon nano-tubes and two dimensional graphene to deionized water
along with a surfactant in an amount ranging from 0.0005 to 0.002 in an unltrasonication
bath for a period fanging from 5to 10minutes; and subjecting the dispersions to probe
sonication for a period ranging from 10 to 15 minutes.
10 The dispersion process (Digital ultrasonication bath, Labman-4,100W) is carried out with
the help of a surfactant for 0.001% of carbaneous materials of carbon nanotubes and
graphene with particle size ranging from 3 to 50 nm in de-ionized water, varying the
particle size and composition first through ultra-sonication using the ultrasonic bath for 10
minutes followed by the probe sonication (PCI ANALYTICS PVT. LTD., Model PKS -
15 750F Frequency (KHZ): 20, Power (W): 750) for around 20 minutes. Typically, the
surfactant is selected from the group consisting of anionic surfactant Sodium dodecyl
benzene sulfonate (SDBS), cationic surfactant, Cetyltrimethylammonium bromide (CTAB)
and non-ionic surfactant, Triton X-100.
This step is further followed by addition of the noble metal nanoparticle colloidal solution
20 to the surface modified aqueous dispersion of the carbon nanoparticles in equal ratio. The
presence of positively charged nanoparticles ( Ag/Pd) nano particles arrange themselves
uniformly across the carbon nano tube and whereas the negatively charged nanoparticle (
Au/Pt)nanoparticles are intercalated in the layers of the 2 dimensional graphene
nanoparticles confirmed through transmission electron microscope analysis. The resulting
25 compositions of CNT-Ag/Pd and Graphene-Au/Pt are kept separately in the hot air oven at
a temperature of 120°C for 6 to 12 hours. The powder sample obtained after this step is
added to the positive and negative active material paste respectively.
The samples are deposited on TEM grids coated with a thin carbon or polymeric support
film; since the film is amorphous, thin (~20 nm) and has a relatively low electron density, it
30 provides a uniform substrate for imaging samples. A small drop of solution is placed onto a
grid and allowed to evaporate, typically under vacuum. The sample is imaged by taking
digital pictures of several locations on the grid to obtain a representative set of images.
Sample survey – Images are captured at a range of magnifications (typically 2,000-
150,000kx magnification, as appropriate for a given sample) to provide data for generating
35 size and shape statistics on the sample, as well as higher magnification of images.
The positive plate of the lead acid battery is covered with a paste of lead dioxide (positive
active material) and the negative plate is covered with a paste of sponge lead (negative
active material), with an insulating material (separator) in between. Typically, the carbon
40 nanomatrix composite(CNT-Ag/Pd, graphene-Au/Pt) present in the positive and negative
active materials of the present invention are one dimensional Carbon Nanotubes dopped
with Ag/Pd and two dimensional graphene dopped with Au/Pt with a particle size lesser
than 50nm, preferably below 20 nm which result in relatively higher enhancement in the
7
electrochemical properties of the Lead Acid Battery. The positive 5 and negative active
materials for the lead acid battery are doped with 0.001 % Carbon nanocomposite (CNTAg/
Pd)and Graphene nanocomposite ( G-Au/Pt) respectively. The surface charge of these
carbonaceous nanoparticles is modified as required by the experiment through the use of
surfactants, which also enhance the stability of the nano-particles and lead to a uniform
10 distribution of the nanoparticles throughout the carbonaceous matrix.
Pasting is a process in which prepared paste is integrated with the grid to produce a battery
plate. This process is carried out through extrusion, and the paste is pressed by machine in
to grid interstices. Paste preparation carried out using lead oxide which is fed in to a mixing
machine and then addition of water and H2SO4 (sulphuric acid) solution are added under
15 by constant stirring condition, during this stage basic lead sulfates are formed. After
defined period of mixing the paste is used for production of positive plates and negative
plates simultaneously, for the negative plates pasting is prepared in similar way, but
addition of expanders along with the mixtures. Once the paste is checked for density and
consistency then pasted into the grids by using specially designed pasting machines.
20 This could increase the power density of lead acid batteries significantly, The improvement
and cyclic performance of the battery cell attributed to the Carbaneous nano-matrix and
noble nano metals as addition to active materials and also improved the texture of the paste
vise versa generated a spongy texture which will help the transporation of the sulphate ions
during the charge discharge process.
25 Pasting is a process in which prepared paste is integrated with the grid to produce a battery
plate carried out separately by marking treated and control for the manufacturing and
assembling. This process is carried out through extrusion, and the paste is pressed by
machine in to grid interstices. The lead oxide is fed in to a mixing machine during mixture
of lead oxide dried carbonaceous nano matrix which contains one dimensional carbon nano
30 tubes with silver noble metal particulate at 0.001% w/v around 30-50nm average size of
nano matrix has been added and then water and H2SO4(Sulphuric acid) solution are added
under continuous stirring. Basic lead sulfates are formed during this stage.
After defined period of mixing the paste is used for production of positive plates. The paste
for negative plates is prepared in similar way, addition of carbonaceous nano matrix which
35 contains two dimensional graphene with noble metal particulate of gold nano particles are
added 0.001% w/v in an average size of 30 -50 nm of carbaneous nano-matrix along with
the expanders added to the mixture.
The paste is checked for density and consistency. The pasted plates are separately passed
through uncoated and coated a flash drying oven to dry the plate (grids) and to remove the
40 moisture on plate surface prior to stacking and eventually arranged in the racks. Followed
by curing process is designed to make the paste bond with the grid and also to make the
8
paste porous materialto improve the formation. Racks with plates 5 are placed in the
curingchambers with 95% humidity for specified time and then dried, during this process
paste get converted into phase composition. The battery assembly process which includes
the series of steps, group stacking, alignment, group burning, group alignment, group
insertion, inspection, terminal alignment, internal short circuit testing check, intercell
10 welding, shear testing, case cover sealing, leak testing, and packed separately based on the
identification marks for the testing parametrs.
In another aspect of the present invention, there is provided a lead acid battery with
improved performance prepared by the method of the present invention. The lead acid
battery of the present invention comprises positive active materials (PAM) and negative
15 active materials(NAM) of the battery doped with nano-composites in an amount ranging
from 0.001 to 0.1% wt. Typically, the nano composites comprise functionalized
carbonaceous matrix comprising carbon nano-tubes with a particle size ranging from 10
to20nm functionalized with positively charged nano-particulate silver and palladium
metals and functionalized carbonaceous matrix comprising two dimensional graphene
20 material with a particle size ranging from 3 to 5nm functionilized with negatively charged
gold and platinum nano-particles respetively.
TESTS :
CAPACITY TEST:
The foolproof indicators/tools for knowing and predicting the health and life of a lead acid
25 battery have yet not been evolved or devised. The only way to truly determine the health of
a standby lead-acid battery is to perform a 100 % capacity test, However, comprehensive
controllers and instruments are now able to find failing cells without this test and while the
battery system is online.The lead acid battery (12 v 35Ah SLI batteries) with the doped
positive and negative active materials is subjected to the Capacity test as per the standard
30 protocol JIS D 5301: 2006 by using the equipment UBT (Universal Battery Tester)
10/40/60/100-18-14 Me – 2014001938, (Digatron power electronics. Aachen, Germany).
With increased rates of discharge the chemical reaction is not fast enough to hold up the
voltage. So there is loss in capacity from C20 to C1. Important tests are C20, C10, C5, C3
and C1. Discharge current for C20 is 100 % capacity, but for C5 capacity loss up to 80%.
35 So C20 current for discharge is 100/20=5 A. and for c5 it is 0.8*C20/5=16 A. The capacity
test shown performance improvement in C1 15.8%,C5 3.9% ,C3- 5.84%, C10 4.83% over
untreated control paste batteries shown in Fig..5A –D
Traction Performance Test:
The performance of the lead acid traction battery analyzed using (12 v 210Ah TRACTION
40 battery) both the treated Carbaneous nano matrix and untreated separately by using
standard protocol (IS 5154,PART 1 : 2013, with the help of Digatron power electronics,
9
Aachen, Germany, HEW 1500-012-Me – 201400519) units during 5 the evaluation. Since it
is important test for calculating the C5 values, the CN reference value quoted by the
manufacturer cell/battery temperature at 30 °C, a discharge time of 5 h, and a cut-off
voltage Uf = 1,70 V per cell. The corresponding discharge current is IN(A)=CN(Ah)/5(h)
noted .
10 The actual capacity Ca shall be determined by discharging a fully-charged battery. The
resultant value is used for the verification of the nominal capacity CN. To facilitate the
temperature readings, one pilot cell is selected per group of six cells, the average of the
pilot cells being considered as representative of the average temperature of the battery. The
temperature of each pilot cell shall be read immediately prior to the discharge. The
15 individual readings shall be between 15 °C and 40 °C. The average initial cell temperature
t0 is calculated as the arithmetic mean of the individual values.
Within 1 h to 24 h after the end of charging, the battery shall be subjected to a discharge at
the current IN. This current shall be maintained constant within ±1 % throughout the whole
discharge time.
20 If the initial temperature t0 is different from the reference temperature (30 °C), the capacity
C, shall be corrected to the actual capacity Ca by the equation:
Ca = C/(1+ ?1 (t0-tr)).
where
t0is the initial temperature;
25 tr is the reference temperature (30 °C);
?1 = 0,006 (°C)–1 for the 5 h capacity.
The performance analysis of the traction batteries shown in Fig.6 which reveals 6.55%
improved in traction cyclic test over the untreated control batch batteries shown in FIG.6
30
WATER LOSS TEST
The water loss test procedure conducted for the treated and untreated control battery using
lead acid starter type battery using JIS-D5 301: 2006 standard. The test procedure
conducted using (Universal Battery tester 10/40/60/100-18-14 Me-2014001938) The
35 completion of charging clean and dry the surface of the batter,and take the weight the mass
of the battery using(12v 35Ah SLI battery),Digatron power Electronics,Aachen, Germany.
The battery shall be placed in the water bath at 40± 2°C. The water surface should be
15mm to 25mm below the upper surface of the battery, then charge the battery with
14.4V+0.05V measures the battery terminal for period of 500h.Immediately after the
40 overcharging of the battery clean and dry the surface of the battery and calculate the
weight. The water loss performance was 33% improvement over the control untreated
battery shown in Fig.7TEM
10
5 EXAMPLES
CONTROL:1-
The Pasting is a process in which prepared paste is integrated with the grid to produce a
battery plate carried out for the manufacturing and assembling. This process is carried out
through extrusion, and the paste is pressed by machine in to grid interstices. The lead oxide
10 is fed in to a mixing machine along with water and H2SO4 (Sulphuric acid) solution are
added under continuous stirring. Basic lead sulfates are formed during this stage. After
defined period of 45 mins mixing the paste is used for production of positive plates. The
paste for negative plates is prepared in similar way, addition with the expanders into to the
mixture. The paste is checked for density and consistency. The battery assembly process
15 which includes the series of steps, group stacking, alignment, group burning, group
alignment, group insertion, inspection, terminal alignment, internal short circuit testing
check, inter-cell welding, shear testing, case cover sealing, leak testing, and packed
separately based on the identification marks for the following testing parameters.
SEM ANALYSIS:
20 POSTIVE ACTIVE MATERIALS: FIGURE 4 A confirms the agglomerated (clumps)
particles
NEGATIVE ACTIVE MATERIALS:4 C confirms the agglomerated (clumps) particles
EFFICIENCY TEST- Power Battery
? Capacity test – C 1, C3,C5,C10
25 TRACTION BATTERY PERFORMANCE-
? Capacity performance- C5
WATER LOSS TEST
? 2 %
30 EXAMPLE2: PREPARATION OF POSTIVE ACTIVE MATERIALS USING 1-D
CARBON NANO TUBE WITH NOBLE METALS USING SURFACTANTANTCTAB:
Preparation of Carbaneous nano matrix using Carbon nano tube with the average particle
size of 30 -50 nm with the concentration 0.001 % is added and sonicated with positive
11
surfactant CTAB to modify the surface charges to positive. So that 5 it will bind with the
positively charged noble metals like silver/palladium used, the surface modification was
carried out using Ultra sonication process by probe method with the addition of0.001 % of
CTAB for the period of 10mns.Along with dispersed the solution addition of 10-3 molar
concentration of 30-50nm of noble metal colloidal solution added in the Carbaneous nano
10 matrix. The dispersed solution kept for observation over the period of 2-3 hours. The
following observation parameters noted which given below.
OBSERVATION:
NON-UNIFORM DISPERSED SOLUTION
FORMATION AGGLOMERATION
15 PRECIPATATION OBDERVED
INFERENCE:
I. After the conversion of positive charges on the surface, the Noble nanoparticles
were not connected due to the repulsive nature as both the sides having positive
charges.
20 II. Carbon nanotubes dispersed into the medium but noble metals not interconnected
with the matrix medium.
RESULTS:This process not optimized for the manufacturing the batteries.
EXAMPLE 3: PREPARATION OF POSTIVE ACTIVE MATERIALS USING 1-D
CARBON NANO TUBE WITH NOBLE METALS USING SURFACTANTANT-
25 :SDBSPreparation
of Carbaneous nano matrix using carbon nano tubes with an average size
particle of size 30-50nm with the concentration 0.001 % is added and sonicated with
negative surfactant to modify the surface charges to negative. The surface modification was
carried out for negatively charged surface medium with negative charge surfactant using
30 Ultra sonication process by probe sonication method with the addition of 0.001 % of SDBS
for the period of 10mns. The uniform dispersion solution was collected and addition of 10-3
molar concentration of positively charged noble metal like silver/palladium of 30-50nm of
an average size into the dispersed medium and allowed to dry for period of 10-12hrs at
800C in the hot air oven. The dried powder Carbaneous materials carbon nano tube with
35 noble metals were added to the positively active materials paste during the manufacturing
process and battery assembled tested for the following parameters.
SEM ANALYSIS
12
POSTIVE ACTIVE MATERIALS PASTE( 5 Figure 4 A) – Clumps observance
POSTIVE ACTIVE MATERIALS PASTE WITH CARBON NANO TUBE( Figure 4B –
Observance of CNT decorated with Silver Noble metal enhances the porous nature of the
active material)
TEM ANALYSIS:
10 NOBLE METALS PARTICLES (Figure 2 C observance of Noble nano particle Silver)
CARBON NANOTUBE MATRIX DECORATED WITH NOBELE METALS( Figure 2 D
observance of CNT decorated with Silver Noble metal)
COLLAIDAL SOLUTION AND CARBON NANO MATRIX:
? Uniform dispersion
15 ? Agglomeration not observed
? Precipitation not observed after 24 hrs
? Carbon nano-matrix dried fine powder obtained without any lumps
INFERENCE:
The surface matrix is negatively charged which enhanced the binding behavior or due to
20 van der waals forces of attraction along with positively charged Noble nanoparticles such
as Silver and palladium.
EXAMPLE 4:PREPARATION OF POSTIVE ACTIVE MATERIALS USING 1-D
CARBON NANO TUBE WITH NOBLE METALS USING SURFACTANTANT-
:TRITON X-100-
25 Preparation of Carbonaceous nano matrix using carbon nano tubes with an average size
particle of size 30-50nm with the concentration 0.001 % was added and sonicated with
neutral surfactant. The surface modification was carried out for neutral charged surface
medium with neutral charge surfactant using Ultra sonication process by probe sonication
method with the addition of 0.001 % of Triton X-100 for the period of 10mns. The uniform
30 dispersion solution was collected and addition of 10-3 molar concentration of positively
charged noble metal like silver/palladium of 30-50nm of an average size into the dispersed
medium.The dispersed solution was kept for observation over the period of 2-3 hours. The
following observation parameters noted :
OBSERVATION:
35 NON-UNIFORM DISPERSED SOLUTION
13
FORMATION 5 AGGLOMERATION
PRECIPATATION OBDERVED
INFERENCE:
Since the surface of the Carbonaceous nano particle CNT was not modified with any of the
amine or carboxyl group so the CNT based nanoparticle exhibited a repulsive behavior
10 against the Noble nano particle.
RESULTS:This process was not found to be optimized for the manufacturing the
batteries.
EXPERIMENT:
EXAMPLE 5: PREPERATION OF NEGATIVE ACTIVE MATRIX USING
15 CARBANEOUS MATRIX 2 DIMENSIONAL GRAPHENE WITH NOBLE
METALS NEGATIVELY CHARGED: USING SURFACTANT CTABPreparation
of Carbonaceous nano-matrix using Graphene with particle size 3 – 10 nm with
the concentration 0.001 % was added and sonicated with positive surfactant CTAB to
modify the surface charges of positive charged materials, so that it could bind easily with
20 negatively charged noble metal nanoparticles such as gold/palladium/ platinum. The
surface modification was carried out using Ultra sonication process by probe method with
the addition of 0.001 % of CTAB for the period of 10mns. The uniform dispersion was
collected and dried at 80° C using hot air oven for the period of 6-8hrs. The dried powder
was added in to the negative active material with the percentage of 0.001 % w/v. The
25 carbonaceous nano matrix contains Graphene with incorporation of noble nanoparticles
with average size of 30-50nm with concentration of 103 molar concentration were added to
the negative active materials paste during the manufacturing process and assembled battery
tested for the following parameters which given below
SEM ANALYSIS:
30 NEGATIVE ACTIVE MATERIALS PASTE (Figure 4 C)- Observance of Clumsy
particles
NEGATIVE ACTIVE MATERIALS PASTE WITH CARBANEOUS NANO MATRIX
(Figure 4 D)- Observance of discrete graphene decorated with Noble nano metal.
TEM ANALYSIS:
35 NOBLE METAL PARTICLES (Figure 3 C Au – Gold Noble metal)
14
GRAPHENE MATRIX DECOORATED WITH NOBLE METALS 5 (Figure 3 D Graphene
with Noble Metal)
COLLADIAL SOLUTION AND CARBON NANO MATRIX:
? Uniform dispersion
? Agglomeration not observed
10 ? Precipitation not observed after 24 hrs
? Carbon nano-matrix dried fine powder obtained without any lumps
EXAMPLE 6: PREPERATION OF NEGATIVE ACTIVE MATRIX USING
CARBANEOUS MATRIX 2D GRAPHENE WITH NOBLE METALS
NEGATIVELY CHARGED: USING SURFACTANTANT-SDBS15
Preparation of Carbaneous nano-matrix using graphene with particle size 3 – 10 nm with
the concentration 0.001 % was added and sonicated with Negative surfactant SDBS were
used to modify the surface charges to negative charged materials to verify the behavior of
the surfactant. The surface modification was carried out using Ultra sonication process by
probe method with the addition of 0 .001 % of SDBS for the period of 10mns. Along with
20 dispersed the solution addition of 10-3 molar concentration of 30-50nm of noble metal
colloidal solution added in the Carbaneous nano matrix. The dispersed solution kept for
observation for the period of 2-3 hours. The following observation parameters noted which
given below.
OBSERVATION:
25 NON-UNIFORM DISPERSED SOLUTION
FORMATION AGGLOMERATION
PRECIPATATION OBDERVED
INTERFERENCE:
I. Carbaneous Nanomatrix and Noble metal Nanoparticle due to weak in bonding
30 started settling in the bottom.
II. Surfaces charges of the nano-matrix are in negative state the Noble Nanoparticle
was not having significant bonding with the negatively charged noble metals such
as gold / platinum and this is mainly due to the repulsive behavior or vander-waals
forces of the noble metal nanoparticle.
35
RESULTS: This process not optimized for the manufacturing the batteries.
15
5
EXAMPLE 7: PREPERATION OF NEGATIVE ACTIVE MATRIX USING
CARBANEOUS MATRIX 2D GRAPHENE WITH NOBLE METALS
NEGATIVELY CHARGED USING SURFACTANT TRITON X-100-
Preparation of Carbonaceous nano-matrix using graphene with particle size 3 – 10 nm with
the concentration 0.001 % is added and sonicated with neutral 10 surfactant triton-X-100 used
to understand the binding nature Carbaneous nano-matrix with noble metals particulate.
The dispersion technique was carried out using Ultra sonication by probe method process
with the addition of 0.001 % of Triton X-100 for the period of 10mns. Along with
dispersed solution the addition of 103 molar concentration of 30-50nm of noble metal
15 colloidal solution added in the Carbaneous nano matrix. The dispersed solution kept for
observation for the period of 2-3 hours. The following observation parameters noted which
given below.
OBSERVATION:
NON-UNIFORM DISPERSED SOLUTION
20 FORMATION AGGLOMERATION
PRECIPATATION OBDERVED
INTERFERNCE:
I. Absence of optimal medium to support the noble metal nano particles with
carbonaceous graphene.
25 II. The surface of the carbonaceous graphene is not modified with any of the amine or
carboxyl group so the graphene based materials having a repulsive behavior against
the Noble nano-particles.
RESULTS: This process not optimized for the manufacturing the batteries.
30 OUTCOME OF THE EXPERIMENTS:
The example experiments of 3 & 5 optimized for manufacturing battery since the Nano
composite formed well with noble metals. The Batteries were manufactured as per the
above procedure and tested for following parameters:
Power Battery: Capacity Test (C1 , C3, C5 & C10)
35 Traction Battery: Performance analysis & Water Loss.
16
5
References in the specification to “one embodiment”, “an embodiment”, “another
embodiment, “a preferred embodiment”, “an alternative embodiment”, “one variation”, “a
variation” and similar phrases mean that a particular feature, structure, or characteristic
described in connection with the embodiment or variation, is included in at least an
embodiment or variation of the invention. The phrase “10 in one embodiment”, “in one
variation” or similar phrases, as used in various places in the specification, are not
necessarily meant to refer to the same embodiment or the same variation.
While the foregoing examples are illustrative of the principles of the present invention one
or more particular applications, it will be apparent to those of ordinary skill in the art that
15 numerous modifications in form, usage and details of implementation can be made without
the exercise of inventive faculty, and without departing from the principles and concepts of
the present invention. Accordingly, it is not intended that the present invention be limited.
Furthermore, the described features, structures, or characteristics may be combined in any
suitable manner in one or more embodiments. In the description, numerous specific details
20 are provided, such as examples of lengths, widths, shapes, etc., to provide a thorough
understanding of embodiments of the present invention. One skilled in the relevant art will
recognize, however, that the invention can be practiced without one or more of the specific
details, or with other methods, components, materials, etc. In other instances, well-known
structures, materials, or operations are not shown or described in detail to avoid obscuring
aspects of the present invention. ,CLAIMS:We claim:
1. A method of improving the performance of a lead acid battery; said method
comprising the following steps :
a. preparing a first and a second dispersion of nano-particulate carbenous materials
comprising one dimensional carbon nanotubes and two dimensional graphene
respectively;
b. preparing a first and a second colloidal solutions of nano-particulate noble metals
comprising positively charged and negatively charged noble metal particles
respectively;
c. preparing a first and a second carbenous nano-composites by adding the first and
15 second dispersions of nano-particulate carbenous material to the first and second
colloidal solutions of nano-particulate noble metals;
d. heating the first and second nano-composites in an hot air oven at a temperature
ranging from 80 to 1100C for a period ranging from 7 hours to 12 hours. to obtain
the first and second nano-composites in powder form;
e. doping positive active material and negative active material with the first and
second nano-composites in poweder form respectively;
f. loading the doped postive and negative active materials in the battery grid to obtain
a battery with improved performance.
2. A method as claimed in claim 1, wherein the particle size of carbon-nano tubes used
25 for making the first dispersion of nano-particulate carbonaceous material ranges
from 30 to 50nm
3. A method as claimed in claim 1, wherein the particle size of two dimensional
graphene used for making the second dispersion of nano-particulate carbonaceous
material ranges from 3 to 5nm
30 4. A method as claimed in claim 1, wherein the two dimensional graphene particles
used for making the second dispersion of nano-particulate carbonaceous material
are characterized by average lateral size varying from about 5 to about 10 microns
and surface area ranging from about 250 to 300 m2/g.
5. A method as claimed in claim1, wherein the positively charged nanno-particulate
35 noble metals are silver and palladium while the negatively charged nannoparticulate
noble metals are gold and platinum; the particle size of both the
psotively charged and negatively charged noble metal particles being in the range
from 10 nm to 50nm.
6. A method as claimed in claim 1, wherein the method step of preparing a colloidal
40 dispersion of nano-particulate noble metals comprises the following steps:
? providing an aqueous precursor solution of noble metals with a molar
concentration ranging from 10-2M to 10-4M in ultra-purified distilled water;
? preparing an extract of lemon grass by boiling lemon grass in distilled water;
18
? heating the aqueous precursor solution at a temperature 5 ranging from 50 to700 C
under continuous stirring and adding the extract of lemon grass to the boiling
precursor solution under stirring in an amount ranging between 5 to 10% and
? verifying the formation of colloidal dispersion by observing the color change.
7. A method as claimed in claim 1, wherein the method step of preparaing the first and
10 second dispersion of nano-particulate carbenous materials comprises :
dispersing a nano-particulate carbonaceous material selected from the group
consisting of one dimensional carbon nano-tubes and two dimensional graphene to
deionized water along with a surfactant in an amount ranging from 0.0005 to 0.002
in an unltrasonication bath for a period fanging from 5to 10minutes; and
15 subjecting the dispersions to probe sonication for a period ranging from 10 to 15
minutes.
8. A method as claimed in claim 7, wherein the surfactant is selected from the group
consisting of anionic surfactant Sodium dodecyl benzene sulfonate (SDBS),
cationic surfactant, Cetyltrimethylammonium bromide (CTAB) and non-ionic
20 surfactant, Triton X-100.
9. A method as claimed in claim 1, wherein the postive active material and the
negative active material is doped with the first nano-composite and second nanocomposite
respectively in an amount ranging from 0.001 to 0.1% w/w
10. A lead acid battery with improved performance prepared by the method of the
25 present invention comprising poistive and negative active materials doped with
nano-composites in an amount ranging from 0.001 to 0.1% wt; said nano
composites comprising functionalized carbonaceous matrix comprising carbon
nano-tubes with a particle size ranging from 10 to20nm functionalized with
positively charged nano-particulate silver and palladium metals and functionalized
30 carbonaceous matrix comprising two dimensional graphene material with a particle
size ranging from 3 to 5nm functionilized with negatively charged gold and
platinum nano-particles respetively.
Dated this 31st Day of March, 2017.