Title: Lithium Batteries for Implantable Biomedical Devices Chemistry and Applications
1Lithium Batteries for Implantable Biomedical
Devices Chemistry and Applications
Presented at the Indiana University Department of
Chemistry, March 18, 2008
- Curtis F. Holmes, Ph.D.
- Greatbatch, Incorporated
2Greatbatch, Incorporated
The company was founded in 1970 by Mr. Wilson
Greatbatch, an electrical engineer and the
co-inventor of the cardiac pacemaker, Mr.
Greatbatch believed in 1970 that the remaining
problem to be solved for the pacemaker was the
battery. He licensed the lithium/iodine
technology, hired experienced battery
scientists, and marketed the lithium/iodine
battery to the pacemaker industry. By 1977,
virtually all pacemakers were powered by lithium
batteries. The company has grown through
acquisition and market growth. Sales in 2006
were gt 270 million. There are 2200 employees at
present.
3Critical Component Supplier
Batteries
Feedthroughs
Engineered Components
Capacitors
EMI Filters
Value Add Assembly
Commercial Batteries
Coated Electrodes
Enclosures
4Interaction of electrical stimulation and body
tissue
- It has been known since the 1700s that
interesting phenomena occur when electrical
signals are applied to body tissues. These
phenomena have led to the development of devices
that treat diseases by stimulation of muscle or
nerve tissues.
- In 1780, Luigi Galvani, working at the
University of Bologna, found that the electric
current delivered by a Leyden jar or a rotating
static electricity generator would cause the
contraction of the muscles in the leg of a frog
and many other animals, either by applying the
charge to the muscle or to the nerve.
5Implantable Devices
- Cardiac Rhythm Management
- Neurostimulation
- Drug Delivery
- Hearing Improvement
- Left Ventricular Assist Devices/Totally
Artificial Heart
6Cardiac Rhythm Management
- Bradycardia
- 1960s - today
- Tachycardia/Ventricular Fibrillation
- 1980s - today
- Congestive Heart Failure
- 2000s
7What does a pacemaker cure?
- We all have a pacemaker! - The heart's "natural"
pacemaker is called the sinoatrial (SA) node or
sinus node. It's a small mass of specialized
cells in the top of the heart's right atrium
(upper chamber). It generates the electrical
impulses that cause the heart to beat. - The natural pacemaker may be defective
(Stokes-Adams syndrome), causing the heartbeat to
be too fast, too slow or irregular. The heart's
electrical pathways also may be blocked. A
patient with a heart beat of less than 60 BPM is
said to have bradycardia. A heart rhythm that
is too slow can cause fatigue, dizziness,
lightheadedness, fainting or near-fainting
spells. - Patients suffering from bradycardia need an
artificial pacemaker to supply the same
electrical impulses that the sinoatrial node
provides in healthy people. - Over 900,000 pacemakers per year are implanted
worldwide. - The first successful cardiac pacemaker, invented
by Mr. Wilson Greatbatch and Dr. William
Chardack, was assembled in Clarence, NY and
implanted into a patient at the Veterans
Hospital in Buffalo in 1960.
8External Pacemaker Montefiore Hospital in 1958
The gentleman in this photograph, taken at the
Montefiore Hospital in New York in 1958, is Mr.
Pincus Shapiro. He is pushing a Zoll external
pacemaker. The device was connected to his heart
via a catheter that was implanted from Mr.
Shapiros left arm into his right ventricle. The
second electrode was embedded under the skin in
his chest. The boundaries of Mr. Shapiros world
were determined by the length of the extension
cord connecting his pacemaker to the wall socket.
9Implantable Pacemaker History
- In 1958, Wilson Greatbatch designed and
built an implantable pacemaker in his modest
laboratory in Clarence, NY. He spent two years
experimenting with dogs. In 1960, the first
successful pacemaker in the United States was
made by him and implanted in a patient at the
Veterans Hospital in Buffalo. The surgeon was
Dr. William Chardack, who had worked with
Greatbatch to develop the device. Greatbatch
licensed his invention to a company called
Medtronic, now the worlds largest producer of
implantable devices, and that was the start of
the implantable device industry. Today many
hundreds of thousands of pacemakers are implanted
each year.
Dr. Chardack, Dr. Gage, and Mr. Greatbatch - 1960
Wilson Greatbatch today
10Implantable Pacemaker History
- Implantable pacemakers were also developed
(independently) by Dr. Ake Senning and Dr. Rune
Elmqvist in Sweden and Dr. Orestes Fiandra in
Uruguay. Sennings invention led to the
founding of a company called Siemens Elema, now
part of St. Jude Medical, in Stockholm. Fiandra
founded a company called Centro de Construccion
de Cardioestimuladores del Uruguay (CCC) in
Montevideo, Uruguay. Both companies are
Greatbatch customers today.
- The first person to receive an internal pacemaker
was Arne H. W. Larsson (1915 2001), an engineer
in Sweden. Larsson lived until the age of 86,
used a total of 26 pacemakers, and was a
well-known personality in the world of cardiac
pacing he often attended international
pacemaker conferences as a guest of Siemens
Elema. His device worked for only 3 days, and he
remained unpaced until receiving a
properly-operating device 3 years later.
Arne Larsson
11Early 1960s - Ten Batteries, two transistors!
12Modern Pacemaker One battery, thousands of
transistors
13The Implantable Cardioverter/Defibrillator
What does it cure?
- Ventricular tachycardia - a potentially lethal
disruption of normal heartbeat that may cause the
heart to become unable to pump adequate blood
through the body. The heart rate may be 160 to
240 (normal is 60 to 100 beats per minute).
Uncontrolled, it can lead to ventricular
fibrillation. - Ventricular fibrillation - a condition in which
the heart's electrical activity becomes totally
disordered. When this happens, the heart's lower
(pumping) chambers contract in a rapid,
unsynchronized way. (The ventricles "flutter"
rather than beat.) The heart pumps little or no
blood. The outcome of this condition, absent
appropriate therapy, is both obvious and grim.
14History of the ICD
- The ICD was invented by Dr. Michel Mirowski (1924
- 1990) at the Johns Hopkins University in 1979. - A dear friend and colleague of Dr. Mirowski had
died of VF, and Mirowski believed that the
disease could be treated by implanting a
battery-powered device that detected VF and
shocked the heart back into normal sinus rhythm.
With Dr. Martin Mower and Dr. Stephen Heilman,
Mirowski developed the first ICD, and it was
produced by a company called Intec Systems (which
was later acquired by Guidant).
- His idea was met with skepticism, criticism
(an English physician claimed it was unethical)
and, at the 1979 International Pacemaker
Conference in Montreal, with ridicule (When he
showed a movie of a dog that had been implanted
with a defibrillator and was revived from an
induced VF, someone asked him how long it had
taken him to train the dog to do that trick).
- But of course he was right Hundreds of
thousands are implanted today.
15ICD - 1989
16ICD 1998 Transvenous lead
17ICD 2007
The Ovatio ICD is produced by Sorin Group (ELA
Medical). With a volume of 29 cm3, it is the
smallest ICD currently on the market. It has
been approved for sale in the U. S. and in
Europe. The small size and rounded,
pacemaker-like shape of the device can be
attributed to the Greatbatch capacitor and
battery technology. Greatbatch also supplies
filtered feedthroughs and cases for the device.
18Congestive Heart Failure (CHF)
- CHF is a condition in which the heart's function
as a pump is inadequate to meet the body's needs.
It can be treated by a technique called
biventricular pacing. - It involves pacing in both ventricles - known as
resynchronization. - Historical note the first clinical trials of
biventricular pacing were done using two
pacemakers, since no one had developed a
pacemaker capable of pacing both ventricles! - Most devices also have ICD capability.
- Studies have demonstrated that this is a
promising new approach to the treatment of CHF
19Neurostimulation What does it treat?
- Pain
- Incontinence
- Parkinsons Disease
- Epilepsy
- Spasticity
- Obesity
- Depression (in clinical trials)
20Cyberonics Vagus Nerve Stimulator
This device treats epilepsy through vagus nerve
stimulation and is much more effective than drug
therapy.
21Implantable Drug Delivery What does it provide?
- Chemotherapy
- Pain Relief
- Treatment of Diabetes
- Treatment of Cerebral Palsy
- Treatment of Multiple Sclerosis
22Implantable Drug Delivery Device
23Implantable Hearing Devices
- This technology treats Serious Hearing Loss with
a totally-implantable device
24Otologics Hearing Device
The Otologics Implantable Hearing Device
Tiny Greatbatch feedthroughs are used in the
Otologics device
25Left Ventricular Assist Device
The left ventricle is the large, muscular chamber
of the heart that pumps blood out to the body. A
left ventricular assist device (LVAD) is a
battery-operated, mechanical pump-type device
that is surgically implanted. It helps maintain
the pumping ability of a heart that can't
effectively work on its own. A typical LVAD has a
tube that pulls blood from the left ventricle
into a pump. The pump then sends blood into the
aorta (the large blood vessel leaving the left
ventricle). This effectively helps the weakened
ventricle.
26What is a battery (electrochemical cell)?
- Battery means a device consisting of one
or more electrically connected electrochemical
cells which is designed to receive, store, and
deliver electric energy. An electrochemical cell
is a self-contained system consisting of an
anode, cathode, and an electrolyte, plus such
connections (electrical and mechanical) as may be
needed to allow the cell to deliver or receive
electrical energy. - -
Federal Government Definition
27Basic Cell
28The Baghdad Battery
A 2,200-year-old clay jar found near Baghdad,
Iraq in 1936, has been described as the oldest
known electric battery in existence. The clay jar
and others like it have been attributed to the
Parthian Empire an ancient Asian culture that
ruled most of the Middle East from 247 B.C. to
A.D. 228. It is thought that the battery was
used to electroplate jewelry objects with gold
The nondescript earthen jar is only 5½ inches
high by 3 inches across. The opening was sealed
with an asphalt plug, which held in place a
copper sheet, rolled into a tube. This tube was
capped at the bottom with a copper disc held in
place by more asphalt. A narrow iron rod was
stuck through the upper asphalt plug and hung
down into the center of the copper tube not
touching any part of it.
29The Voltaic pile
- In 1799, Alessandro Volta (1745 1827) arranged
a vertical pile of metal discs (zinc with copper
or silver) and separated them from each other
with paperboard discs that had been soaked in
saline solution. This stack became known as the
voltaic pile and was the progenitor for modern
batteries. The French word for battery is la
pile.
30Cell Chemistry and Thermodynamics
- Cell Voltage
- Cathode materials and anode materials have
different electrochemical potentials, determined
by thermodynamics - The cell open circuit voltage (OCV) represents
the difference of cathode and anode
electrochemical potentials. The OCV of the
battery is determined by the Gibbs Free Energy of
the battery reaction, according the following
equation - ?G -nF Eº ?H - T ? S
- where ?G is the Gibbs Free Energy, n is the
number of moles transferred in the cell reaction,
F is the Faraday Constant (96,500 coul/mole),
and Eº is the OCV. - ?S (nF) ? Eº
- ? T
31Cell Chemistry and Thermodynamics
- Important Battery Properties
- Capacity (Ampere hours) ?0t Idt
- Energy (Watt hours) ?0t E.Idt
- Power (Watts) E.I
- where I is current, E is voltage, and
t is time.
32Types of Lithium Implantable Medical Batteries
- Lithium/Iodine
- Lithium/CFx
- Lithium/Silver Vanadium Oxide (SVO)
- Lithium/Manganese Dioxide
- Q Technologies
- High Rate QHR
- Medium Rate QMR
- Lithium/Hybrid (CFx and SVO Mixture)
- Lithium Ion Rechargeable
33Types of Lithium Implantable Medical Batteries
- Two Battery Systems will be discussed in detail
in this presentation the Lithium/Iodine
pacemaker battery and the Lithium/Silver Vanadium
Oxide Defibrillator Battery.
34Batteries for Pacemakers
- The lithium/iodine battery was developed and
patented by scientists at Catalyst Research
Corporation in the early 1970s. Their invention
was based on work done at the Jet Propulsion
Laboratory in the late 1960s and published in
the Journal of the Electrochemical Society. Mr.
Wilson Greatbatch licensed the fundamental
patents from CRC and, with battery scientists
Ralph Mead and Frank Rudolph, invented and
patented many improvements (e. g., anode coating
and the case-grounded design). - The first lithium/iodine cell was implanted in
Italy in April 1972. Before that time,
pacemakers were powered by zinc/mercuric oxide
batteries that were short-lived, unreliable,
unpredictable, and discharged hydrogen gas. - Since that time, millions of cells have been
implanted. - Most pacemakers currently being implanted use
lithium/iodine cells, although some advanced
pacemakers are using Li/CFx, lithium hybrid
cathode batteries, and QMR cells.
35Batteries for Pacemakers
- April 2007 marked the 35th anniversary of the
first implant of a pacemaker powered by a
Li/Iodine battery. The implant occurred in
Italy. - Since that time, millions of cells have been
implanted. - Although several lithium-based chemical systems
have seen use in pacemakers (silver chromate,
cupric sulfide, thionyl chloride, manganese
dioxide, titanium disulfide), the lithium/iodine
battery became the only remaining pacemaker
battery technology until the introduction of
liquid electrolyte batteries such as Li/CFx and
the hybrid battery (mixed CFx and silver
vanadium oxide) in the last few years. It
remains the most widely-used pacemaker battery
today. - The battery has compiled a remarkable record of
reliability and predictable performance. - It is arguably the first successful
commercialization of a lithium-anode battery. - It will continue to be used for the foreseeable
future.
36The Lithium/Iodine battery
- One could argue that, based on standard battery
performance criteria, its not a very good
battery! - It cant start a car, run a cell phone, or even
power a flashlight. - It has very high internal resistance
- It doesnt work well when its cold.
- It doesnt work well when its too hot (above
55C). - Temperatures above 60C will permanently damage
the cell. It explodes like a bomb at 180.5ºC
(the melting point of lithium). - Its not inexpensive to manufacture.
- BUT Put it at 37C and ask it to provide 10
50 microamperes of current, and it will do it
reliably for many years.
37The Lithium/Iodine Battery
- It has been said that it is a very elegant
battery system - Elegant in its simplicity
- Simple cell reaction
- Straightforward cell design
- Elegant in its complexity
- Very complicated interactions among iodine, PVP,
and lithium - Performance shows a very strong dependence on
cell discharge current - Elegant in its performance record
- Remarkable record of reliability and usefulness
for 35 years.
38Lithium/Iodine Battery
39Lithium Anode
-
- Atomic Number 3 Atomic Mass 6.941 amu
- Melting Point 180.54 C Boiling Point
1347.0 CNumber of Protons/Electrons 3 Number
of Neutrons 4 Classification Alkali Metal
Crystal Structure Cubic Density _at_ 293 K 0.53
g/cm3 Color silvery - Ionization Potential 5.39 eV
- Electrochemical Equivalent 3.86 Ah/Gram
- Trivia Note Lithium metal is one of only two
materials that react with elemental nitrogen at
room temperature (if humidity is present)!
40Anode Coating
- In the early 1970s it was discovered by
Greatbatch scientists that coating the anode with
PVP dissolved in a volatile solvent greatly
affected the performance of the cell. The
coating was done with a camels-hair paint brush.
The PVP was dissolved in tetrahydrofuran and
painted onto the anode. The THF was dried, and
the PVP remained on the anode. This improvement
was patented in 1976 (patent Number 3,957,533) - The coating has a profound positive effect on the
discharge characteristics of the cell. - Studies at Medtronic in the 1980s showed that
the coating led to the formation of a yellow
liquid exhibiting ionic conductivity during
discharge, contributing to the observed
improvement in cell performance. - In 1987 a substrate coating method was developed.
It is a much more efficient way of coating the
anode and results in much more uniform coating
weights and cell performance.
41Comparison of discharge curves of uncoated and
coated anode cells
42Lithium Iodide Electrolyte/Separator
- Ionic Salt
- Density 3.494 gr/cm3
- Lithium Ion Conductivity 10-7 S/cm
- Negligible Electronic Conductivity
- Negligible Iodide ion conductivity
- Self-forming, Self-healing
- Structure greatly modified by coating the anode
with PVP
43The Iodine/Polyvinylpyridine (PVP) cathode
material
The Iodine/PVP material is formed by a thermal
reaction between iodine and PVP. The reaction
occurs above the melting point of iodine
(113C). This thermal reaction is exothermic
and produces a tar-like material that melts
slightly below the melting point of iodine. At
the 30/1 weight ratio used at Greatbatch, the
material is mostly elemental iodine at unit
thermodynamic activity, with a small amount of
the reaction product of iodine with PVP
44DSC of Formation of the Cathode Material
45Phase Diagram of the Iodine/PVP Material
dotted line is 37 C
As the cell is discharged, the cathode material
transitions from region 6 through region 5, and
finally to region 4. Region 6 is a 2-phase system
containing the eutectic melt and pure iodine.
Region 5 is a single phase liquid material.
Region 4 is a two-phase system wherein the
one-to-one iodine/monomer unit adduct phase
coexists with the melt.
46Conductivity of the Iodine/PVP cathode material
The conductivity of the iodine/PVP material has
been shown to be electronic in nature. Electron
Paramagnetic Resonance spectroscopy of the
cathode material shows a single narrow signal
with a g value of 2.002. This indicates that
there exist free (unpaired) electrons in the
material. The conductivity is a function of the
ratio of iodine to PVP in the material, as shown
in the next slide.
47Conductivity of the Iodine/PVP cathode material
48Thermodynamic Characteristics of the
Lithium/Iodine Reaction (300º K)
- Li ½ I2 ? LiI
-
- ?G ?H - T?S
- From JANAF Thermochemical Tables
- ?G -64.451 kcal/mole
- ?H -64.551 kcal/mole
- T?S -0.101 kcal/mole
- ?G ?H - T?S -nF Eº
- Eº 2.8 volts
- ?S (nF) ? Eº
- ? T
49Lithium/ Iodine Cell Reaction
50Discharge curves of a typical Li/Iodine battery
at various constant resistive loads
51The Selim-Bro Curve
This curve provides a standard method of
predicting battery capacities for a given load.
The curve is formed by plotting the achieved
capacity of a primary battery as a function of
the logarithm of the current drain (ref R. Selim
and P. Bro, Performance Domain Analysis of
Primary Batteries, J. Electrochem. Soc. 118,
829, (1971)). A typical curve takes the general
form of an inverted "U." The capacity is lower
at heavy loads because of polarization, i.e. the
battery is not as efficient because the current
drain is such that the resistivity of the battery
causes the voltage to decline. At lighter loads,
the capacity becomes lower because of
self-discharge.
52(No Transcript)
53The Implantable Cardioverter/Defibrillator
- Treats Ventricular Tachycardia
- Detects Ventricular Fibrillation and administers
shock directly to the heart to restore normal
sinus rhythm
54Batteries for Implantable Cardiac Defibrillators
The lithium/silver vanadium oxide battery
- Scientists at Greatbatch, Inc. developed the
lithium/silver vanadium oxide (Li/SVO) battery
system in 1982. It was adapted for use in the
implantable defibrillator a few years later. - In 1987 the first ICD powered by Li/SVO was
implanted in Sydney, Australia. - Li/SVO has become the technology standard and
most ICDs use the system. - SVO has the ability to deliver high power
- It has high volumetric energy density
55Lithium/Silver Vanadium Oxide Battery
56Silver Vanadium Oxide (SVO)
- Silver Vanadium oxide (Ag2V4O11) belongs to a
class of chemical compounds of somewhat
indeterminate stoichiometry called Vanadium
Oxide Bronzes. - They were first synthesized and studied by
Casalot, Pouchard, and coworkers at the Centre
national de la recherche scientifique in France.
They were interested in the compounds rather
interesting magnetic properties. - SVO can be synthesized via several different
reactions. The reaction used at our company is
the thermal decomposition of Vanadium Pentoxide
and Silver Nitrate - 2V2O5 2AgNO3 ? Ag2V4O11 2NO2 O2
- The compound exists in several phases depending
on the conditions of synthesis.
57Silver Vanadium Oxide Structure
58SEM Image of Silver Vanadium Oxide
59Li/SVO Battery Characteristics
- Cell Reaction Ag2V4O11 7 Li ?
Li7Ag2V4O11 - High Voltage 3.2V
- High Capacity 1.37 Ah/cm3
- High Power 20-30 mA/cm2
- DOD Indication Staged Disch. Profile
- Long Shelf Life Self Disch.lt2/Year
- Safety and Reliability Extensively Tested
- Issues Studied Rdc Growth/V-Delay
60Defibrillator Battery 3-year discharge curve
61Discharge Curve/Cell Reaction first plateau
62Q Technology a brief introduction
- A new cell system has been developed that
provides high energy density, high power and high
stability - A suitable battery technology for next generation
ICDs - Proven technology with patent protection and with
5 years real time cell test data - Flexible and scaleable cell design to meet the
market needs - Mechanistically based performance model developed
to predict battery performance under various
applications
63Q Technology Combining the Carbon Monofluoride
and SVO Chemistries
64Summary
- Over five million people have been implanted with
battery-powered devices. - Devices treat heart problems, pain, epilepsy,
chronic illnesses, hearing loss, and other human
illnesses. - These devices are powered by lithium batteries,
which offer high energy density, reliability, and
longevity. - Significant improvements in battery performance,
electronic circuitry, and electrodes have
permitted newer, smaller devices that perform a
wide variety of functions.