Introduction to the Development of Lithium Batteries in the United States
Sep,12,24
Introduction to the Development of Lithium Batteries in the United States
one
The United States is the most developed country in the world for lithium battery industry. The development history of lithium batteries in the United States is about 50 years, which means that the United States has been developing lithium batteries since the 1950s. Now it has become the country with the largest variety of lithium battery products in the world. Before the 1960s, the main application markets for lithium batteries in the United States were industrial and civilian sectors. During the Cold War period after the 1970s, due to the need for the two superpowers, the United States and the Soviet Union, to strengthen their arms race, the main market for lithium batteries in the United States was military applications. Since the early 1990s, as the arms race between the United States and the Soviet Union weakened, the application direction of lithium batteries in the United States gradually shifted towards industrial and civilian fields. The production of lithium batteries in the United States is mainly reflected in primary lithium batteries, most of which have been commercialized, such as primary lithium batteries Li/SO2, Li/MnO2, Li/I2, and Li/SOCl2. The future development direction of lithium-ion batteries in the United States is to improve high current discharge performance and further seek solutions to safety issues under abusive conditions. The research and development of lithium batteries in the United States mainly focuses on secondary lithium batteries (commonly known as rechargeable batteries, rechargeable batteries, or rechargeable batteries). It was not until the late 1990s that the safety issues of all lithium battery varieties in the United States, including lithium-ion batteries, were basically resolved, and their applications gradually shifted from military to civilian in large quantities. Battery market experts claim that the proportion of military lithium batteries in the United States has decreased to 10% since 2000, far lower than the proportion of civilian lithium batteries. He expects that lithium batteries will be widely used in civilian appliances in the United States in the 21st century, and the prospects are very promising.
Overview of the Development of Lithium Batteries
The development goal of lithium batteries in the United States is to replace 15% of the traditional batteries currently used. To achieve this goal, the United States is systematically developing lithium batteries. During the decade from the early 1970s to the early 1980s, the development of lithium batteries in the United States was not rapid. For example, in 1979, the total sales of lithium batteries accounted for 1.6% of the entire battery market, and in 1982 it was 2%. However, production rapidly increased thereafter. In 1987, the total global output value of lithium batteries reached 1 billion US dollars, while in the United States, the output value of 9-volt rectangular primary lithium batteries used for camera flashes alone reached 100 million US dollars, accounting for 10% of the world's total. This indicates that the production of lithium batteries in the United States developed rapidly in the late 1980s. Since 1987, lithium batteries in the United States have grown at a rate of 40% per year. According to application fields, primary lithium batteries in the United States can be divided into the following four areas. The cathodes developed by the United States for producing lithium batteries are listed in Table 1.
Table 1 Cathode series of primary lithium batteries
cathode
series
molecule
amount
Valence
change
density
g/cm3
Theoretical electricity quantity
Ah/g Ah/cm3 g/Ah
SO2
sixty-four
one
one point three seven
0.419 ------- 2.39
SOCl2
one hundred and nineteen
two
one point six three
0.450 ------- 2.22
SO2Cl2
one hundred and thirty-five
two
one point six six
0.397 ------- 2.52
Bi2O3
four hundred and sixty-six
six
eight point five
0.35 2.97 2.86
Bi2Pb2O5
nine hundred and twelve
ten
nine
0.29 2.64 3.41
(CF)2
(31)n
one
two point seven
0.86 2.32 1.16
CuCl2
one hundred and thirty-four point five
two
three point one
0.40 1.22 2.50
CuF2
one hundred and one point six
two
two point nine
0.53 1.52 1.87
CuO
seventy-nine point six
two
six point four
0.67 4.26 1.49
CuS
ninety-five point six
two
four point six
0.56 2.57 1.79
FeS
eighty-seven point nine
two
four point eight
0.61 2.95 1.64
FeS2
one hundred and nineteen point nine
four
four point nine
0.89 4.35 1.12
MnO2
eighty-six point nine
one
five
0.31 1.54 3.22
MoO3
one hundred and forty-three
one
four point five
0.19 0.84 5.26
Ni3S2
two hundred and forty
four
0.47 2.12
AgCl
one hundred and forty-three point three
one
five point six
0.19 1.04 5.26
Ag2CrO4
three hundred and thirty-one point eight
two
five point six
0.16 0.90 6.25
V2O5
one hundred and eighty-one point nine
one
three point six
0.15 0.53 6.66
2.1 Military lithium batteries
2.1.1 Thermal battery
This type of battery is a primary reserve battery developed by the United States in the 1970s. The anodes used in the production of thermal batteries in the United States are metal Li, Li Al, Li-B, and Li Si alloys. The cathodes used are FeS2 and CuCl2, etc. The outstanding feature of this type of battery is the use of LiCl KCl molten salt as the electrolyte. The most ideal application is in the military industry, such as being used as a power source for shells, rockets, bombs, missiles, false targets, jamming aircraft, naval torpedoes, and nuclear weapons. Among them, LiAl/FeS2 and LiSi/FeS2 batteries have been successfully applied in missiles, nuclear weapons, and artillery. The typical thermal battery produced in the United States is LiSi/FeS2, with one model weighing 2700g, a volume of 652cm3, a working voltage of 24-36V, a working current of 3.1A, and a lifespan of 13min. The performance development goals for lithium batteries for missiles formulated by the US Marine Weapons Center are listed in Table 2. From the table, it can be seen that the development goals of thermal batteries for naval missiles are all lithium batteries. This indicates that the United States attaches great importance to the development of lithium batteries.
Table 2 Performance Objectives of Navy Missile Lithium Batteries
Battery production
Compared to energy
Wh/kg
Specific power
W/kg
Work life
Ming Ming
Storage life years
application
Now: Calcium series thermal battery
twenty-two
eight hundred and eighty
0．17~5
fifteen
Missile fuse
Projectile fuse
Goal: Lithium anode thermal battery
eighty-nine
two thousand six hundred and forty
0．33~20
twenty
Missile fuse
Projectile fuse
Now: Zinc silver battery, calcium
Series of thermal batteries
22~44
six hundred and sixty
2~15
5~15
Missile guidance
And control
Goal: Room temperature lithium battery
Lithium anode thermal battery
88~440
three thousand and three hundred
2~30
10~20
Missile Guidance and Control
2.1.2L/V2O5 battery
This type of battery is a one-time reserve battery at room temperature. The cathode is composed of 90wt% V2O5 and 10wt% graphite, with an electrolyte of 2mol/ LLiAsF6 or 0.4mol/ LLiBF4 methyl formate solution, with a non-woven polypropylene membrane as the diaphragm and a stainless steel shell. The structural forms are buckle type, carbon wrapped cylindrical type, and square type. This series is mostly used as a power source for small projectile fuses and for certain special purposes. The main production company is Honeywell in the United States. The comparison between Li/V2O5 and Li/SOCl2 batteries in the United States is listed in Table 3.
2.1.3 Li/SO2, Li/SOCl2, and Li/SO2Cl2 batteries
All three types of batteries belong to primary reserve batteries. Li/SO2 batteries are known as advanced batteries in the United States and are one of the main lithium battery products in the country. Li/SOCl2 batteries have high production capacity and the fastest growth rate, making them the most energy-efficient battery series in practical applications in the United States. Military large capacity batteries can reach 500Wh/kg (900Wh/L). Li/SO2Cl2 batteries have potential advantages over Li/SOCl2 batteries. The only difference between the former and the latter is the SO2Cl2 with carbon and adhesive on the nickel or stainless steel mesh of the cathode. The materials and properties used for the three types of batteries are listed in Table 4.
Table 3 Performance Comparison of Li/V2O5 and Li/SOCl2 Batteries in the United States
Battery
temperature
℃
Voltage
V
capacity
mAh
volume
cm3
weight
g
Compared to energy
Wh/kg Wh/L
Li/V2O5
G2659 type
-37~57
-37~57
three point one five
three point three zero
one hundred and sixty
one hundred and eighty
five point one
five point one
ten
ten
50.4 98.8
59.4 116.5
Li/SOCl2
G26591B1 type
-37~57
-37~57
three point zero five
three point six zero
three hundred
four hundred and fifty
five point one
five point one
ten point five
ten point five
87.1 179.4
154.3 317.6
Table 4 Comparison of Materials and Properties Used in Three Types of Batteries
Battery
Li/SO2
Li/SOCl2
Li/SO2Cl2
cathode
Carbon on aluminum mesh
SO2 in adhesive
Strip on nickel mesh or stainless steel mesh
SOCl2 with carbon and adhesive
SO2Cl2
electrolyte
Acetonitrile (AN)/LiBr
SOCl2+LiAlCl4
SOCl2+LiAlCl4
the diaphragm
polypropylene
Glass felt or fiber paper
Glass felt or fiber paper
Shell
Nickel plated steel
Nickel plated steel or stainless steel
Nickel plated steel or stainless steel
Working voltage, V
2.7~2.9(20℃)
Roll up cylindrical battery above 3V
Specific energy, Wh/kg
two hundred and eighty
Large capacity batteries with a capacity of 500
Working temperature, ℃
-55~70
-40~70
-40~70
Applicable models
cylindrical
Square, flat round, and cylindrical shapes
spiral wound
Main applications
Military portable monitor
Wireless transceiver
Large 10000Ah battery used for missiles
Launch shaft as power source
Military field
Main manufacturers
Duracell co.,et.al
Union Carbide, GTE, Altus, and Ho-
Neywell's Four Companies
Willson-Greatbatch、
GTE Company
1. Lithium batteries for industrial electronic instruments
2.2.1Li/SOCl2 battery
The Li/SOCl2 battery with a cylindrical structure and small current discharge is used in this field as a power source for storage devices, instruments, and small electronic devices. The materials, processes, and manufacturers used in the production of this type of battery in the United States are the same as those used in large capacity Li/SOCl2 batteries (see Table 4).
2.2.2L/MnO2 battery
The materials and properties used in the production of this type of battery in the United States are listed in Table 5. This type of battery is safe to use, does not pollute the environment, has low cost, and can compete with traditional batteries in price. Therefore, it is the first commercialized solid cathode lithium battery in the United States. At present, it is mainly used for storage, calculators, and high-power electronic devices such as motor drives.
Table 5 Materials and Properties of Li/MnO2 Batteries
Structural components and performance items
Component materials and performance data
cathode
MnO2 coated with adhesive on the skeleton
electrolyte
Solvent PC+DME, solute LiClO4
Shell
Battery companies use nickel plated steel or stainless steel
the diaphragm
polypropylene
Applicable models
Only suitable for making coins or cylindrical shapes
Working voltage (20 ℃), V
2．7~2.8
Specific energy, Wh/kg
two hundred
Working temperature, ℃
-20~55
Storage life (25 ℃), years
five
Manufacturer's structural type
Coin type, coiled cylindrical type
Manufacturer
duracell
2.2.3 Li/(CF) n battery
This type of battery is produced by Eagle picher company and is also a solid cathode primary lithium battery marketed in the United States. Its appeal lies in its long storage life. Low power batteries can be used as power sources for printed circuit board installation, while button batteries can be used as DC power sources for calculators and storage devices. Small capacity needle type batteries can be used as power sources for light-emitting diodes and microelectronic devices, while large cylindrical and square batteries can also be used as power sources for radio receivers, telemetry devices, and photography equipment. Kodak's disc-shaped camera uses BR2/3 batteries (Table 6).
Table 6 Li/(CF) n Battery Materials and Properties
Structural components and performance items
Component materials and performance data
cathode
CF with carbon and adhesive on nickel skeleton
electrolyte
Solvent: BL+THF, PC+DME;
Solute: LiAsF6, LiBF4
Shell
Nickel plated steel or stainless steel
the diaphragm
polypropylene
Applicable models
Suitable for making buckle and cylindrical shapes (up to 5Ah)
Working voltage, V
2.6~2.7
Specific energy, Wh/kg
two hundred
Working temperature, ℃
-20~60
Main applications
Industrial electronic instruments
Manufacturer's structural type
Most of them are buckle type, but there are also cylindrical types
Manufacturer
Eagle-picher
2.2.4 Li/Ag4CrO2 battery
The cathode of this battery is Ag4CrO2 sheet with added carbon, the electrolyte solvent is propylene carbonate, the solute is LiClO4, the diaphragm is polypropylene, the shell is nickel plated steel or stainless steel, the working voltage is 2.5-3.2V, the specific energy is 275Wh/kg, and the working temperature is -10~55 ℃. The characteristics are high volume to energy ratio, high cost, and long storage life. It can be made into flat or button type, square and D-type batteries. In the application of low rate discharge storage devices that require high reliability, long shelf life, and working time exceeding 10 years, their high price is acceptable. It was once used in the medical field and is now mainly used in industrial appliances.
2.2.5 Li/CrOx battery
This type of battery is suitable for making 1/2AA type batteries, and can also be made into cylindrical carbon pack structures. Its characteristics are high voltage, high specific energy, and low rate discharge capability. Therefore, it is designated for use in electronic instruments under low rate discharge conditions.
3 Lithium batteries for medical use
The lithium batteries used in this field are mainly Li/I2 solid electrolyte lithium batteries. This type of battery was first developed in Italy. In the late 1960s, the Catalyst Research and Development Corporation (CRC) in the United States began developing this type of room temperature battery. In the early 1970s, the first generation product was designed and produced, and it was found to be very effective for use in pacemakers. It can be said that the application of this type of battery brought a revolution to the pacemakers at that time. Currently, 85% of the 350000 pacemakers produced worldwide use Li/I2 batteries. Its working temperature is 25 ℃, the electrolyte is LiI (Al2O3), and the cathode is Pb S、PbS、PbI2、TiS2。 Most of the previously used Li/Ag4CrO2, Li/SOCl2, Li/Pb, Li/CuS, and Li/MnO2 batteries have been phased out. The manufacturers and specifications of Li/I2 batteries in the United States are listed in Table 7.
Table 7: Manufacturers and Specifications of Li/I2 Batteries in the United States
manufactor
model
Capacity (Ah)
Weight (g)
Volume (cm3)
Length x Width x Height (mm)
application
CRC
802/35
three point eight
fifty-four
eighteen point seven
45x13.5x35
pacemaker
CRC
901/23
two point five
twenty-six
seven point four
45x9.3x23
ditto
WGL
761/15
one point three
seventeen
four point six
45x8.6x15
ditto
WGL
761/23
two point five
twenty-seven
seven point six
45x8.6x23
ditto
WGL
762M
two point five
twenty-nine
eight point two
45x8x28
ditto
CRC
S23p-15
zero point one two
three point eight
zero point eight three
23dx1.8
Pacemaker (button type)
CRC
S19p-20
zero point one two
two point eight
zero point five seven
19dx2.0
ditto
4 civilian lithium batteries
The lithium batteries produced in the United States for this field include Li/(CF) n, Li/MnO2, Li/FeS, and Li/FeS2 batteries. The materials, processes, and manufacturers used in the production of the first two types of batteries are exactly the same as those used in lithium batteries for industrial electronic instruments mentioned above. These four battery series are mainly used as power sources for watches, calculators, cameras, photographic flashlights, toys, and small electronic devices for civilian use. The rated voltage of Li/FeS and Li/FeS2 battery series is 1.5V, with a flat or buckle structure, high impedance, low power, good low-temperature performance and storage performance, and low cost. The United Carbide Corporation and Eveready Corporation produce these two types of batteries mainly to replace the zinc/silver oxide batteries and zinc/mercury oxide batteries that were previously used in watches, calculators, and cameras.
5 Development Trends of Lithium Batteries
The development trend of lithium batteries in the United States is reflected in the changes in the application market. Table 8 in Section 3 of this report indicates that the proportion of military lithium batteries has decreased to 15%, far lower than that of civilian lithium batteries. This is the overall trend of lithium battery development; The second trend is that as the application market shifts from military to civilian use, the capacity and models of lithium batteries have changed from large capacity to small capacity; The third trend is that with the continuous improvement of the material living standards in the United States, the number of cardiovascular disease patients is increasing, and about one in 300 people in the United States needs to install a pacemaker. Currently, 80% of the lithium batteries used in pacemakers are Li/I2 batteries, indicating a large sales volume and a significant growth trend; The fourth trend is that the market for traditional lithium batteries in wireless communication applications has gradually been dominated by high-performance lithium-ion batteries. If the safety issues of lithium-ion batteries are thoroughly resolved, they will be widely used in various fields and replace traditional lithium-ion batteries in larger quantities.
