METHOD OF INCREASING SECONDARY POWER SOURCE CAPACITY
Technical Field
The invention relates to electrical engineering and can be used at
secondary power source capacity manufacturing: accumulators, storage
batteries, and modules, used both in the capacity of power source to
machines, electrical vehicles, and other transport vehicles and cargo
transports, and for portable and mobile electronic devices.
Background Art
At present, secondary power sources are subdivided into a few types,
according to materials that used for them, and running chemical reactions.
Secondary power sources (hereinafter also referred to as batteries) run
on the principle of a summarized current-generating reaction. Energy is
accumulated in a battery under charging from an external power source,
because of a chemical reaction under discharge, the energy again directly
turns into electrical energy and released to the external circuit. In addition,
after the discharge the battery can again be charged by means of backward
passage of current.
Following types of batteries are basic and the most used: the lead acid,
the nickel-metal-hydride, the lithium-ion, and the lithium-polymeric.
Thus, lead dioxide (PbOz) and lead (Pb) are used as reagents; sulphuric
acid solution is an electrolyte in lead batteries. Such batteries are used for
supply of major power consuiners, including production equipment, starting
internal-combustion engines operation, emergency lighting systems, and
uninterruptible power systems. ~ k a d acid batteries have low-cost
manufacturing and durability. Low specific energy., poor charge preservation,
hydrogen loss, impossibility of storage in discharged state, problem with
manufacturing of compact batteries should be reckoned among their
deficiencies.
In nickel-metal-hydride batteries (Ni-MH), intermetallic semiconductor
is an active material of negative electrode, reversibly sorbing hydrogen, i.e.
the negative electrode is actually a hydrogen electrode, reduced hydrogen of
which has the state of absorption. They're used for portable devices and
hardware supply.
In lithium-ion batteries (Li-ion) carbonic material is used as negative
electrode, into which lithium ions are reversibly penetrated. Lithium solution
in a non-aqueous aprotic solvent is an electrolyte. Batteries have high specific
energy, long life, and are able to operate at low temperatures. Due to big
capacity, their output dramatically increased, and lithium-ion batteries have
become one of the most prospective research trends on battery refinement.
That particular type of batteries is used at mobile phones, notebooks, and
other portable devices.
Lithium-polymeric batteries (Li-pol) have also become common use, in
which carbonic material is used as the plate, into which lithium ions are
reversibly penetrated. Vanadium, cobalt, and manganese are active materials
for positive electrodes. Either lithium solution in non-aqueous aprotic
solvents, enclosed in fine-pored polymeric matrix or a polymer
(polyacrylonitrile, polimethyl methacrylate, polyvinylchloride, and others),
plasticized by Lithium solution in an aprotic solvent (gel-polymeric
electrolyte). Compared to lithium-ion batteries, lithium-polymeric batteries
have higher capacity and are also used for portable electronic devices supply.
It should be mentioned that various chemical compositions are devised
for electrodes, electrolytes, and membranes, and for every type of batteries.
Completeness and speeds of running chemical reactions in batteries are
conditioned by such materials, their compositions and structure.
With the lapse of time, major electrical and operational characteristics
of batteries are changed because of irreversible processes, running within
them, both under operation and at their storage.
The main task of development is improvement of electrical and
operational characteristics of batteries.
Generally, ways of the improvement are determined by need for
reducing of above mentioned irreversible processes efficiency on them.
Doping to major chemical composition of an electrolyte or an electrode
is one of basic ways. Such doping makes it possible to block secondary
processes or reduce their influence on major current-generating reactions
running.
Thus, electrolyte doping (US5962164, 05.10.1999; US5780183,
14.07.1998; US2003/0228525 Al, 11.12.2003) is proposed to improve
operational characteristics of lead-acid batteries. Such doping prevents
alterations of electrodes paste, connected with intensive gassing and internal
resistance growth at their sulfatation. Certain additives prevent sulfatation,
formation of large crystals of lead sulfate that prevent running of reversible
current-generating processes in full measure.
Polyaclylamide, an additive to electrolyte, content of which in
electrolyte raises viscosity of electrolyte and keeps powdery pastes and
resultants on electrodes surfaces (RU2257647, 27.07.2005), is also used for
improvement of alkali nickel batteries operational and electrical
characteristics.
There's a certain metal-organic additive doped into a lithium-ion
battery electrolyte, improving its operation stability and increasing the
number of chargeldischarge cycles (US7217477, 15.05.2007). The metalorganic
additive makes it possible to escape excess voltage on electrodes,
using insulating layer formation on cathode surface. The surface of a cathode
active material is controlled by the additive; otherwise, side reactions with the
electrolyte run on it. There are certain additives of carbonate type, doped into
the lithium-ion batte~y electrolyte composition, making possible increasing
the number of chargeldischarge cycles and providing a battery operation both
at room and lowered temperatures (EP1215746, 19.06.2002).
Essentially, the purpose of above mentioned doping is to make it
possible to run the current-generating reaction in full measure. Such .additives
can make possible batteries operation with characteristics that are extreme to
their operating components materials (electrolyte and electrodes), and support
the batteries operation under conditions, regulated by the types of batteries.
Disclosure of Invention
Secondary power source capacity increasing generally stipulated by
materials of its constructs, charge time reduction, and life time increase, is a
technical result, this invention is intended at.
The specified result is achieved by means of the method of secondary
~jower source capacity increasing including doping a compound into an
electrolyte as an additive which binding energy is higher than binding energy
of combinations that are formed at a secondary power source discharge, the
compound of type ANBl0-, is doped as an additive, where A is a metal and
B is a noble gas.
In a articular case a compound of type AzB, is doped as a catalytic
additive in nano-quantity, the molecular structure of which matches the
molecular structure of the additive of type ANBIO-N.
In a particular case the method including an impact on an electrolyte
with electrostatic field, moreover, the vector of the electrostatic field is
parallel to the vector of a charge discharge current, and the intensity rate is set
and supported in the range from 1.000 to 70.000VIcm.
In a particular case the method including a voltage pulse impact on an
electrolyte, the amplitude of which exceeds the value of energetic barrier
width of current-generating chemical reaction, the duration exceeds energetic
barrier width of current-generating chemical reaction, and the pulse-repetition
interval is less or equal to relaxation time of this reaction.
The investigation, carried out by the authors since 1970s and
concerning double and triple connections of intermetallic semiconductors,
their structure, properties, and methods of their synthesis, is taken as a basis
of the applied invention. Descriptions and the results of the investigation are
written in the following works: "Characteristic Features of the Electronic
Spectrum and the Stability of Ternary Diamond-Like Semiconductors".
Phys.Stat.Sol.(b) 90, p.733-740, 1978, A.M.Altshuler, Yu.Kh.Vekilov and
G.R.Umarov M "The stability of the inert AzBs compaunds". Phys.Lett.A, 73,
Nc3, p.216-217, 1979, A.M.Altshuler, Yu.Kh.Vekilov and G.R.Umarov. Such
characteristics of the specified connections, as binding energy, the features of
the crystal structure, symmetry, the impact of adding those compositions on
mobility of ions at electrolyte. The results of investigation and laboratory
research made it possible to find a technical solution intended to achievement
of the above mentioned technical result.
To get to the heart of the applied method, scientific information is
specified below, including that derived from the works, in which the authors
of the invention participated.
Current in electrolyte is a moving of positive and negative ions in
opposite directions, because of an electrochemical reaction, running within it.
Therewith, formation and electrochemical bindings and ruptures run with
energy release and absorption, respectively. As a rule, the energy is generally
used at power sources.
Chemical combinations have a binding energy, as known of physical
chemistry. The binding energy is a difference between dull energy of the
bound state of a co~nbinationa s a system of particles and energy of state in
which the particles are infinitely far form each other and solid-state.
A number of compounds, possessing high binding energy, is marked
out and studied by the authors of the invention within the bounds of the above
mentioned investigation. On the assumption of the fact that the higher binding
energy, the higher energy released at a composition formation, a possibility of
activation of combination reactions and dissociation of mentioned
combinations, in parallel with major current-generating reactions, to use an
energy released under the formation of those combinations, to increase a
battery capacity, is proven by the authors of the invention.
As you know, the quantum-mechanical mechanism of phase
transformations has big practical importance to phase transitions, particularly
under electrical chemical reactions. Examination of the picture of valence
electrons and ions movement under first-kind phase transitions .and quantummechanical
accounts of real agents' energetic spectra made it possible to
precisely show certain classes of agents and the specific process flow which,
in aggregate, made it possible lo achieve considerable improvement of
consumer characteristic of the final product, in this case, secondary power
source capacity increasing.
The start point is based on a number of published works in which the
authors of this invention participated, including, except the above-mentioned,
"Pressure impact on electronic structure of semiconductofs", G. P. Umarov,
V. I. Kozlov, and A. A. Firsanov, High-pressure physics and engineering, rel.
23-1986-p. 9-13, and "The first-kind phase transition mechanisms in metals
and semiconductors under influence of an electrostatic field", G. R. Umarov,
High-pressure physics and engineering, rel. 33-1990-p. 10-14. They affirm
that first-kind phase transitions start on lines of parent phase absolute
fluctuation. Such a fluctuation is a thermodynamic characteristic of the phase
system and, in turn, directly connected with degeneration at the energetic
spectrum of the system at the quantized level, where the levels, occupied with
valent quasi-electrons, have the same value, as energy levels that free of those
quasi-particles. That means that the valence band top in the central point of
Brillouin zone for investigated combinations is found at the bonom level of a
valent conduction zone in medium points of the Brillouin zone border. Thus,
it's obvious that not just the energy conservation law plays an important part,
but also the momentum conservation law directly connecting the internal
symmetry of the start phase with the end phase symmetry through the quasimomentum
symmetry between degenerated levels in real energetic spectra.
("The solution to many-body problems", G. P. Umarov and F. F. Firsanov,
Rasplavi USSR Academy of Sciences. - 1990. 3 - pp. 25-3 1).
The results of the investigation preceded the invention changed
understanding of a number of processes essence and guided the' authors to the
idea of possibility to use the results at effective range to solve problems with
enhancement of secondary power sources. Analysis of the investigation
results made it possible to directly enter experimental design and designs
manufacturing.
The authors as well managed to prove the theorem of a control
structure, or a subsystem, existence that realizes a phase transition. It is
proven that there cannot be another mechanism of ions and quasi-electrons
movement at condensed medium.
For amorphous bodies and liquids that in most cases are electrolytes in
storage batteries, starting internal symmetry is described by means of
structure factor expansion in a generalized Fourier series. In such a case,
deviations f?om the ideal starting structure are the control structure. Averaged
structure factor at the ideal structure contains no uneven degree to ions
deviations of balances. In particular, that means to the crystalline solid that a
phase transition is impossible in an ideal defect-free crystal, free fiom
contamination. In the last case, the role of the control structure is performed
either by vacancies, or by dislocations, or by chemical impurities, or by all
these factors, depending on their relative concentration and polarizability of
their small hydrogen-like levels, weakly binding charge carriers - quasielectrons
and ionic complexes.
It's well known that a battery capacity determined with physicalchemical
processes under electrochemical reactions at charging and
discharging the battery, directly connected with a quantity and concentration
of quasi-free charge carriers, as well as their mobility. Therefore, it's possible
to dramatically increase a quantity of charges in electrolyte, using
combinations (compounds) as an additive to electrolyte with binding energy
which is higher than binding energy of combinations (compounds) generated
at discharge of a battery. For such combinations eight valent electrons and a
contingent of positively charged ions fit a base unit. Binding energy of such
combinations, as well as valence bands depth and exclusion bands width that
strongly correlates to binding energy, is much higher than, for example, at
combinations generated at discharge of a battery (e.g. lead sulphides that have
all the specified characteristics more than twice worse).
Within electrolytes at batteries of the existing types, an irregularity of
charges density is occurred, relative to an average quantity, and there're
coniplexes with a powerful intrinsic charge. Such complexes, at which an
electric charge considerably exceeds a medium charge of ions and complexes
located within electrolyte, having both positive and negative charge, become a
nucleus of a new phase and play the role of the control structure for phase
transitions running. Therewith, the symmetry of the charge configuration in
such nuclei-complexes of the new phase contains symmetry elements of the
new phase. Thus, a sharp polarization of charge carriers within electrolyte
provides dissolution of a combination in it - high binding energy additives, at
which a part of the binding energy is released, and additive charge carriers are
disengaged. The phase transitions, running within the electrolyte, cause
energy storage and the battery capacity increase stipulated by materials of its
constructs.
During the experimentation related to influence of dopes from the range
of compounds with a certain binding energy on secondary power sources
characteristics it is found that it's possible to achieve an additional increase of
charge carrier's mobility within electrolyte which makes it possible to
intensify the process of dope dissolution, release of a part of the binding
energy, and additional charges release. The problem might be solved in
several ways, including their combined use.
It should be noted that control structure concentration, enough for
nucleation of a new phase, is 5-10 degrees less than the great bulk of a
substance. In addition, considering that, for example, the steady-state
concentration of vacancies, playing the role of the control structure within a
solid body, is, as is known, 10'~-10'p~er lcm3, as the base material is
Avogadro number N=6* base units per lcm3, correctly selected additives
in "homeopathic", or rather, nano-quantites, can change the speed, but often
can also change the end result of a phase transition within the major dope. It is
found that the molecular structure of such catalytic dope should match the
molecular structure of the major dope. So, catalytic dopes were
experimentally selected - also compounds of type A&, - which dramatically
intensify the described above processes within electrolyte. Such a catalytic
dope initializes processes in an electrolyte, running by the same mechanism,
as the processes activated with the major dope, but has less energy than the
binding energy of the major dope. However, polarizability of the catalytic
dope combination is high, and it activates the polarizability of the major dope.
It enables more intensive and easy running of dissolution and generation of
new phase nuclei, the catalytic dope plays the role of a catalyst that decreases
the energy barrier of running phase transitions activated with the major dope.
It is experimentally found that it's possible to achieve an additional
mobility increase of charge carriers within an electrolyte, organizing an
electrostatic field or high-voltage pulses impact during charge and/or
discharge of a battery.
Whereas complexes with a charge, markedly differ from an average
one, are nuclei of a new phase, an impact on an electrolyte with an external
electrostatic field or short high-voltage pulses dramatically changes the
activity of charging centers; in addition, the speed grows, energy barrier of
running phase transitions decreases, and the dopes diffusion process within
the electrolyte is activated. Thus, the impact on an electrolyte wit11 an external
electrostatic field or short high-voltage pulses is identical to the impact of a
catalytic dope.
The above mentioned impact is realized as follows. An electrostatic
field is laid over the electrolyte in such a way that the vector of its electric
field is parallel to the vector of a charge discharge current of a battery, and the
intensity rate is set and supported in the range from 1.000 to 70.000V/cm,
depending on specific combination of the major doping to the electrolyte.
Specific intensity rates in the above mentioned range are experimentally
selected to different types of dopes. Electrostatic field might be generated, for
example, by means of voltage supply on a separate isolated and specifically
oriented electrode by electrical circuit galvanically disconnected from the
battery charge/discharge circuit, and the required voltage for ensuring the
specified intensity is received by multiplication of the voltage on the battery
electrodes, according to the known schemas.
It is also experimentally found that the impact on an electrolyte with
high-voltage pulses with a certain amplitude, duration, and porosity leads to
resonance with control structures and additional charging centers release
enables increase of control structure concentration. Such centers absorb
electromagnetic field energy, if the value of the energy matches the
differential between two energy levels of such a charging center. In addition,
higher energy of the charging center means its bigger impact on a phase
transition. Prevention of destructive diffusion processes within a battery that
appear because of an ion barrier formation near electrodes, the electrolyte
internal resistance and the temperature increase, is an additional effect, arising
at the above mentioned impact.
An impact pulse can be generated by means of known schemas of highvoltage
low-current pulse formers, both at charge and discharge of any type
battery. Pulses amplitude is selected to exceed the value of energy barrier AE
of an electrical chemistry current formation reaction and only limited with
electric strength of constructs; duration of pulses is selected to exceed the
value of energy barrier determined as AT - h/ AE, where h is Planck constant,
and the pulse-repetition interval doesn't exceed the relaxation tome of the
above mentioned reaction.
The types of combinations (compounds) and specific dopes structures
exert an effective influence on the structure that controls electrochemical
processes, had been initially rated theoretically. Hereafter, the combinations
of the dopes were experimentally refined, and their optimal concentration
within electrolyte was determined.
Modes for Carrying out the Invention
The examples of realization of the stated method of secondary power
source capacity increasing are given below. Moreover, the comparative
electrical and operational characteristics of lithium-ion batteries (standard
battery and batteries which were manufactured under the claimed method) are
given in table.
Example 1. The following compounds were doped for a standard
lithium-ion battery (the positive electrode is carbonic, the negative electrode
is made of lithium oxide and manganese):
ZnKr (average exclusion bands width of which is E, ,i,,-5,4eV, binding
energy is E,-1,293 Rylatom);
CdAr (E, ,i,,-5,2 eV, E,-1,28 1 Ry/atom);
The doping was added to an electrolyte (up to 8% of the electrolyte
volume) at the battery manufacturing which dissolved within the electrolyte.
The battery is connected to a consumer after the charge of the battery was
made. At power supply it's found that released charge carriers at the doping
dissolution enable 80% growth of the battery capacity.
Example 2. Compound ZnKr was doped into an electrolyte at lithiumion
battexy manufacturing (binding energy E,-5,4 Ry/atom). With that, an
additive electrode that is isolated of the electrolyte and working electrodes,
was placed into the battery design, with respect to which an electrostatic field
with up to 70.000V intensity was generated. For that, voltage applied on the
electrode by electrical circuit galvanically disconnected ffom the battery
major current circuit. The voltage-multiplying circuit of the battery to the
required value was made as a single unit constructively coupled with the
battery and connected to its schemas. As a result, the capacity of the battery
was approximately multiplied by 1,8.
Example 3. Compound ZnKr was doped into an electrolyte at lithiumion
battery manufacturing (binding energy E,-5,4 Ry/atom). With that, a
high-voltage low-current pulses former was added into the battery design,
manufactured as a single unit; the pulses had the following characteristics:
durability is loons, pulse-repetition interval is 80ns, and amplitude is 1.500V.
The outlet of the unit is connected to terminals of the battery. About 90%
increase of the battery capacity is the result.
Thus, as seen from the above mentioned information, doping into an
electrolyte the certain additives and additional impact on received
combination at charging and discharging, according to this invention makes it
possible to considerably increase capacity of a secondary power source,
reduce charging time, and a number of charge discharge cycles, i.e. extend
life time of a battery.
The examples given in the description, illustrate preferable variants of
the announced method realization, however, different realizations are possible
without a deviation of the invention essence within the scope of the proposed
formula.
Industrial Applicability
Experimental models of a few types of batteries were designed under
way of the announced method. Such batteries can be extensively used as
autonomous power sources for electrical machines, transport vehicles,
particularly, electric vehicles, and as a battery to portable and mobile
electronic devices.
Table 1. The spread sheet of lithium-ion secondary power source
electrical and operational characteristics.
Electrical and
operational
characteristics
of battery
Energy density,
W"Jkg
Internal
resistance, mW
Number of
chargeldischarge
cycles till 20%-
capacity loss
Charge rate, hr
dependence
Local action, %,
a month (room
temperature)
Rated voltage,V
Load current,
relating to
capacity C:
- peak
-the most
adoptable
Operating
temperature
range,OC
Standard:
Positive
electrode is
made of
carbon,
negative
electrode is
made of
lithium oxide
and
magnanese
110-160
150-250
500-1000
2-4
D:- very low
10
3,6
>2C
1C and
below
-20 +60
with a major
additive in
electrolyte
ZnKr and organized
additional impact
with external
electrostatic field
2 10-350
140-240
600-1 500
0,l-2
very low
10
38
>2C
0,7-1,l C
-20 +60
with a
major
additive in
electrolyte
ZnKr
(example
3)
180-300
170-260
500-1000
2-3
very low
10
3,7
>2C
0,8-1,0 C
-20 +60
Lithium-ion battery
with a major
additive in
electrolyte
ZnKr and
organized
additional impact
with high-voltage
pulses
(example 5)
160- 190
140-180
600- 1300
0,l-2
very low
10
3,8
>2C
0,7-1,l C
-20 +60

Claims
1. A method of secondary power source capacity increasing, including
doping a compound into an electrolyte as an additive which binding energy is
higher than binding energy of combinations' that are formed at a secondary
power source discharge, the compound of type ANB,+N is doped as an
additive, where A is a metal and B is a noble gas.
2. The method according to claim 1, wherein a compound of type
AzBd is doped as a catalytic additive in nano-quantity, the molecular
structure of which matches the molecular structure of the additive according
to claim 1.
3. The method according to claims 1-2, including an impact on an
electrolyte with electrostatic field, moreover, the vector of the electrostatic
field is parallel to the vector of a charge discharge current, and the intensity
rate is set and supported in the range from 1.000 to 70.000V/cm.
4. The method according to claims 1-2, including a voltage pulse
impact on an electrolyte, the amplitude of which exceeds the value of
energetic barrier width of current-generating chemical reaction, the duration
exceeds energetic barrier width of current-generating chemical reaction, and
the pulse-repetition interval is less or equal to relaxation time of this reaction.
Dated this 02"* Day of April 2014
Of Anannd And Anand Advocates
Agents for the Applicant