This description relates to electrical components that are configured to reduce the effects from fluid exposure and voltage bias.
Electronic devices can include materials configured for behaviors primarily focused on performance of the product and manufacturability. These materials within these electronic devices (and components thereof), however, when exposed to a fluid and when biased to a voltage, can be degraded and/or fail in an undesirable fashion.
In one general aspect, a device can include a housing and an electrical component disposed within the housing. At least a portion of the electrical component can include an active-passive material. The active-passive material can have a passivation range spanning a target bias voltage range of the device.
Electronic devices such as power tools, batteries and battery packs, laptops, motors and/or power supplies rely on materials selected for behaviors primarily focused on performance of the product and manufacturability. For example, the battery industry often uses steel or plated steel for the connections between the cells. In motors, the fine pitch connectors have a voltage bias between each connector, but the connector material can be selected based on its electrical current carrying characteristics and mechanical performance (crimping). Alternating current (AC) to direct current (DC) power supplies can include many potential voltage differences or biased components within the electrical circuitry and select terminals based off electronic conductivity, and manufacturability.
These materials within these electronic devices (and components thereof), however, when exposed to a fluid (e.g., water) and when biased to a voltage (e.g., a DC voltage via a charger, an AC voltage), can fail in an undesirable fashion. In particular, in electronic applications where a voltage bias exists, there is potential for corrosion and other undesirable electrochemical (e.g., electrolysis) reactions when exposed to conductive fluid (e.g., water with dissolved ions). This effect is exacerbated when the voltage bias is greater and there is a higher concentration of electrolyte (for example, a salt dissolved in the water). Seawater or saltwater equivalents can be used to define acceptable behavior when metals under bias are subjected to this condition or other similar electrolytes. These electrolytes are defined as being near neutral pH (e.g., pH of approximately 4-10) with high concentrations of dissolved ion content (≲1M).
Some adverse effects of known materials can include degradation of device life from corrosion of components, added resistance from poor electrical contact or change in material properties, added heat from electrical resistance or undesired reactions, thermal runaway of components including battery, fire, caustic liquid formation, heat/pressure generation, explosion, formation of combustible gas mix thru electrolysis (e.g., H2 and O2), formation of toxic gas (e.g., chlorine, gases that are harmful to breathe, gases that can cause deleterious health including death or cancer), and so forth. For example, electrical devices can be exposed to a fluid including ions that can form an electrolyte between biased (e.g., DC biased) electrical components resulting in fire and explosion. This problem is not specific to batteries or power tools but can be a common problem in products that are electrically powered across a variety of applications and industries.
The selection of material for the electrical component 110, and methods of configuration, described herein, for use in the electrical device 110, generally include at least one or more of the following characteristics:
(1) An active-passive type material (including metals and their alloys)
(2) A passivation range spanning a target bias voltage range
(3) A low energy of formation for corrosion products
(4) An electrolysis reaction inhibitor
At least one or more of the characteristics above can be included in, or used to configure, a material for inclusion in the electrical device 100 to eliminate undesirable release of heat, byproducts, failure, and so forth. Specifically, the characteristics above can be included in, or used to configure a material of the electrical component 110 that will be resistant to fire, explosions, degradation or performance, etc. even if a fluid (e.g., water) infiltrates the electrical device 100 while under voltage bias. The fire, explosions, degradation or performance, etc. can occur in response to, for example, heat when the fluid infiltrates the electrical device 100 while under voltage bias.
As a specific example, the electrical component 110 can be configured to, for example, minimize electrochemical reaction effects in biased components when exposed to fluid (e.g., water with ions). These criteria can be broadly applied to many examples. The electrical component 110 can be, or can include, for example, brass, bronze, silver, and/or similar alloys in an application of 20 volt bias condition with neutral pH saltwater (e.g. such as that experienced in battery pack).
The electrical component 110, and configuration methods thereof, can be advantageous over products (e.g. battery packs) that include elements to mitigate, for example, saltwater effects by taking primarily an extrinsic approach to the problem. Specifically, the electrical component 110, and configuration methods thereof, can be advantageous over methods and apparatus (e.g., industry standard methods of assembly and materials) to address catastrophic or reliability failures in water including, for example, glues, tapes, insulators, geometry (e.g., increased distances between voltages), dielectrics, greases, surface treatments, coatings, and so forth. The electrical component 110, and configuration methods thereof, can also be advantageous over methods and apparatus including the addition of dielectric adhesives, non-conductive insert between connected components, non-wetting (hydrophobic) treatments, package sealing sealed to prevent water intrusion, spacing of connectors (cells in pack) further apart, defining geometry to increase electrolyte path, avoiding use of low impedance cells (that may discharge too quickly in case of external short such as an aqueous based discharge mechanism), avoiding use of high voltage circuits, and so forth.
The problem of prior solutions was not previously fully appreciated and the general assumption was that undesirable failure was due primarily to the conductivity through water (e.g. Joule heating). This is a metal independent issue and a result of the electrolyte conductivity, not the metal's electrochemical or chemical reactivity. According to the present disclosure, the electrical component 100, in contrast, is configured based on an improved comprehension of electrochemical mechanisms including the effects from electrolysis and corrosion reactions. The electrical component 100 is configured based on an understanding of metal surface passivation and the role of metal reaction inhibiting behavior. The electrical component 100 is configured based on the rate of governing half-reactions at anode and cathode, which contribute to conductivity through an aqueous medium or fluid (e.g., saltwater) and generation of heat. Applying these factors to the electrical component 100 (e.g., metal (materials)) selection process has resulted in significant improvements over currently employed techniques.
Stated differently, current practices commonly use materials that are not especially resistant to electrochemical reactions (i.e. corrosion and electrolysis) under exposure to saltwater. Though it is common to use superficial practices that attempt to address the problem, understanding the root causes of the issue (which has not previously been comprehended) guides more appropriate selection of, for example, the electrical component 110 (e.g., a metal connector). For instance, there are currently issues with battery fires and explosions that result from the selection of metals used in their electrical circuitry and their housing materials. These failures have been identified for many years in the industry, but have only been somewhat resolved using superficial practices or result of empirical causality.
Advances in power electronics and new battery technology have led to an increase in DC voltage bias and high power electrical and/or new cordless products that were not previously possible. These high power devices are by design more susceptible to degradation mechanisms or failure from infiltration of aqueous fluids (e.g., water with ions). The corrosion and electrochemical reaction of such components is not commonly studied at such extreme conditions (i.e. far from equilibrium). Often times, reference data does not exist to predict how electrical connectors (e.g., metals) will perform or behave in these conditions. Selection practices outlined in this document attempt to guide this selection in order to minimize electrochemical effects. This effect can be validated with electrical calorimeter test described later to measure electrical energy dissipated through aqueous fluids and resultant generation of heat.
Basing the selection of the electrical component 110 instead on properties such as the varying electrochemical reactivity of different metals can have drastic positive effects on the performance, the heat generation, the safety, and/or the reliability of the electrical component 110. In other words, the properties intrinsic to the electrical component 110 also have a significant effect.
For example, many of the components (e.g., battery pack straps, terminals, conductors) use steel to connect cells together. Steel is particularly poor in its electrochemical reaction resistance to saltwater under bias. Similar issues exist for other common components such as aluminum (large free energy of oxide formation), nickel and copper (good electrolysis catalysts). Other issues with these metals can also exist (e.g., low passivation breakdown potential, no passivation, fast corrosion rate, and preference for chlorine gas formation). By staying within current design criteria for electrical components (e.g., conductivity, cost, strength, and solderability) the electrical component 110 can be configured to meet the desired minimized electrochemical reactivity criteria.
The electrical component 110, and methods of configuration of the electrical components 110, can have advantages including at least reduction or minimization of heat generation, protection of product integrity (e.g., electrical device 100), reduction or limitation of toxic gases, reduce toxic chemical formation, reduction or limitation of combustible products, mitigation of water caused failure, reduction or minimization of shorting of electrical connectors, lessening of effects from electrochemically unstable conditions, addressing of long felt need in the industry, and so forth. In some implementations, the reaction products can generate heat that does not exceed a threshold value determined, by a plastic melting point, a flash point, an electrolyte decomposition, or any critical material or product value associated with the electrical component 110 (e.g., a housing around the electrical component). The relationship can be roughly represented as follows: Heat Accumulated×Specific Heat<Critical Temperature Rise of Electrical Component.
Implementations of the present disclosure include one or more of the following features. The electrical component 110 can have corrosion resistance through stable passivation film formation. The electrical component 110 can have slow reaction rates and minimize heat generated. The electrical component 110 can have passivation film stable to voltages that span a connector high voltage and a nearest low voltage (e.g. difference of 20 volts). The electrical component 110 can have accelerated local corrosion. The electrical component 110 can cause electrical interruption or disconnect.
The electrical component 110 can corrode with a low energy of formation (ΔG) for byproducts (less heat) (e.g. Zinc). The electrical component 110 can have a water channel to direct electrolyte contact in case of exposure. The electrical component 110 can have a low current exchange density. The electrical component 110 can have relatively ineffective (e.g., bad) catalyst to slow electrolysis half-reactions (i.e. reaction inhibitor). The electrical component 110 can have slow corrosion kinetics. The electrical component 110 can minimize galvanic junction with connectors or plating of unalterable metals (e.g. conductor, battery terminal metal to strap metal has minimum ΔV to cause galvanic corrosion). The electrical component 110 can have relatively high conductivity. The electrical component 110 can minimize resistive heating inefficiencies (ideal for electrical connections). The electrical component 110 can have desirable cost, availability, machinability, weldability, solderability, mechanical properties, and so forth. The electrical component 110 can have geometry (e.g. surface area, spacing, etc.) configured for desirable behavior, coatings, counter-acting measures, and so forth.
The electrical component 110 can be configured to conduct electrical current. The electrical component 110 can include a metal that is workable for processing, manufacturing, and assembly of equipment. The electrical component 110 can have ideal strength, elasticity, and thermal coefficient of expansion. In other words, the electrical component 110 can have desirable mechanical properties. The electrical component 110 can include a metal that can be coupled to (e.g., weldable to, joinable to) existing components for simple integration into circuits (e.g. soldering connections should be possible). The electrical component 110 can include a metal that is affordable and/or commercially available so products can be bought/sold for a reasonable price (e.g., in some implementations, gold may be a cost prohibitive solution).
As shown in
In some implementations, when the electrical component 110 is, for example, a connector and is exposed to a fluid such as water, the electrical component 110, or a portion thereof, can change from an active state to a passive state. Changing quickly from the active state to the passive state can be advantageous, in some implementations. Formation of the protective layer 120 (which can be stable) can be critical to limiting electrochemical reaction rates. The protective layer 120 can be chemically bonded to (e.g., chemically formed on) the electrical component 110. A protective layer 120 may be formed in production of part or during infiltration of fluid between biased electrical connectors.
The electrical component 110 can be made of a metal that is not in equilibrium with the ambient environment, and can have a passive state on its surface which allows the electrical component 110 to be more useful in the electrical device 100. The protective layer 120 can inhibit (e.g., prevent) corrosion not only in aggressive chemical mediums but also in fluids (e.g., the moist atmosphere of the earth, fresh water). An active metal material (e.g., lithium and sodium metals) is one which undergoes uninhibited corrosion, and may not have a stable passive state. The electrical component should transition from the active to the passive state. Though most metals used in engineering metals form a thin passive surface film in air (≲100 nm), the state of these surfaces under voltage bias is more strictly defined in the following document. The stability of passive films in air is different from that of passive films in aqueous environments under voltage bias.
The electrical component 110 can be configured to undergo passivation in response to an applied bias. The electrical component 110 can configured to undergo anodic metal passivation in aqueous fluids above a biased voltage potential (e.g., passivation potential energy, Epp, also known as Flade potential). In such implementations, the anodic current of metal dissolution can decrease.
The protective layer 120 can be relatively thin. The protective layer 120 can be a nanometer-thin film (e.g., oxide film) is formed on the active metal anode. The protective layer 120 (e.g., an oxide film) can have a thickness that increases in response to increasing anodic potentials. The protective layer 120 can have a passivation current in the passive state that is controlled by the dissolution rate of the passive layer 120, which can be mostly independent of potential in the range of passivation. The electrical component 110 can have significantly lower corrosion current in the passive region than the active region, though this corrosion current can vary depending on the composition of the electrical component 110. In some implementations, a relatively low corrosion current through the electrical component 110 can be desirable because it can decrease (e.g., minimize) resistive heating, heat from corrosion and electrochemical products, and overall heat generated (e.g., minimize heat from dissipation of battery).
At least some examples of corrosion-resistant materials that can be included in the electrical component 110 can include, for example, copper alloys of the brass and bronze family. This can include, for example, copper alloyed with zinc, tin beryllium, silicon, silver, lead, cobalt, and phosphor, which can have good corrosion resistance when subjected to, for example, salt water conditions. Copper alloys of the brass families C200, C300, and C400 as well as bronze family C500 and C600 can have desirable performance in corrosion resistance while also providing sufficient conductivity, as well as other desirable manufacturing qualities. Copper beryllium of the C170 family can also have desirable corrosion resistance performance (in all cases, 0 can indicate any value from 0-9). Silver and silver alloys can also have favorable corrosion resistance performance. As a specific example, the electrical component 110 can be a material such as C50710, which can have, for example, between 1.7-2.3 atomic %, 0.15 atomic % P, 0.10-0.40 atomic % Ni, with the remainder being Cu. This material can be particularly valuable as the electrical component 110 given that this material satisfies the various criteria described herein.
In some implementations, when the electrical component 110 is biased at 1 Volt vs. SHE (Standard Hydrogen Electrode) and placed in a fluid (e.g., an aqueous electrolyte (salt water)) with neutral pH≈7, some current carrying metals included in the electrical component 110 will passivate in these conditions, while others may not. For example, nickel (Ni) ions will readily dissolve and do not form a protective layer. Conversely, titanium (Ti) oxides including hydroxide terminated forms of the metal surface will form a passive film that does not easily dissolve. The passive film protects the underlying Ti metal atoms from further reaction. Electrical components should be chosen which have ability to form passive films when possible.
As another example, steel and iron will only begin active-passive transition above neutral pH values when biased>−0.6 VSHE (vs. Standard Hydrogen Electrode) as shown in
A wider range of pH where passivation is possible for [Cu] copper as shown in
The electrical component 110 (shown in
The electrical component 110 can be configured to operate in an application with an upper voltage bias below a transpassive potential, or a potential at which passivated metal dissolves. The electrical component 110 can be configured to operate in an application with a lower voltage bias that is above a passivation potential.
The transpassive breakdown potential voltage can be a potential where the passivated metal corrosion rates begin to increase again before rapid dissolution of the anode when potential bias becomes too high or positive—the transpassive state. The rate of corrosion can increase exponentially (log function) with voltage (i.e. according to Tafel equation). The transpassive potential where passivation breakdown begins is critically important and should be higher than the bias applied or expected in normal operation of equipment (e.g., a metal included in the electrical device 100). Generally, it is at least a couple of volts higher so that any slight change in conditions will not lead to uncontrolled electrochemical reactions such as corrosion or the breakdown and dissolution of the passivation layer (e.g., the protective layer 120). However, some metals do not go through a passive state or may be suddenly exposed to potentials which force them directly into the transpassive state.
Below the transpassive potential, in the passivation region, the material (e.g., a metal or alloy included in the electrical component 110) experiences very low areal current densities which are often several orders of magnitude less than the corrosion current density (i.e. current per area). The passivation region may extend over a small span of voltage, may extend over a range including larger spans, or may not exist at all. In this passivation region, the protective layer 120 can function as an insulator or semiconductor. When passivation is present, electrical pathways through the electrolyte are limited and electrochemically reactive surfaces are minimized. It also raises the resistance to conductivity, diffusion or transport, and/or charge transfer. The passivation of metal generally raises electrochemical reaction overpotentials often classified as activation, concentration, and resistance contributions. The protective layer 120, which can be a self-protecting layer, can function as a barrier to the underlying conductive materials (metals) of the electrical component 110. It effectively inhibits electrochemical reactions and reduces the overall current. In the case of a battery, for example, this can slow down the discharge of cells in aqueous conditions.
In some implementations, it may also be desirable (e.g., ideal) if the passivation potential is formed at a bias voltage below what is expected in an application of the electrical device 100. This can be referred to as the lower limit of the passivation region or values of operation greater than the Epp or passivation potential. If operating at a voltage bias below the passivation potential, this is the active electrochemical region and should be avoided. Here, corrosion will proceed and could present significant problems. Therefore, the biased voltages applied should be less than the transpassive potential voltage.
Lines 401 through 403 represent various conditions for the metals C1 through C4. Line 401 represents a reducing condition (e.g., no oxygen, under water). Line 402 represents a moderately oxidizing condition (e.g., with some oxygen present). Line 403 represents a strongly oxidizing condition (e.g., high oxygen partial pressure).
For example, for conditions represented along line 402, the behaviors of the various metals C1 through C4 are described below. Metal C1 does not have a passivation behavior (which is not ideal for the condition represented by line 402). Metal C2 has a low transpassive potential (which is acceptable for the condition represented by line 402). Metal C3 has the lowest current density along the condition represented by line 402. Metal C4 has the highest transpassive voltage along the condition represented by line 402.
The breakdown limit of the protective layer 120 of the electrical component 110 is determined by the application where metals (materials) are used and will correspond to the target (e.g., expected) bias applied to components from a battery of the electrical device 100. For example in
With respect to, for example, battery packs and other (DC) electric power sources, additional measures can be implemented to diminish the electrochemical reactions in addition to, or instead of, metal selection. These can include the control of geometry and/or coatings for electrical components. The applications for the solution to this problem could be especially beneficial to power tools where exposure to outdoor environments is somewhat common for these devices. More details regarding geometry are described in connection with at least, for example,
In some implementations, after the protective layer 120 has been formed, the protective layer 120 can be preserved in a desirable fashion. Specifically, the protective layer 120 can be configured to be preserved. For example, when the protective layer 120 has less than ideal volume change characteristics, the protective layer 120 may not provide continued protection. In contrast, when the protective layer 120 has desirable volume change characteristics, the protective layer 120 can protect underlying metal. This trait can be generally stated by saying the protective layer 120 is formed and preserved in relevant condition (V bias, pH, etc.). There may be other extrinsic factors which cause the passive film not to be preserved even though conditions are favorable (e.g. mechanical force like friction or vibration, presence of strong oxidizer or reducer, complexing agent in electrolyte, turbulent water, unique geometry, localized pitting, and so forth). One characteristic that can be used to determine whether or not the protective layer 120 will be preserved in a desirable fashion is the Pilling-Bedworth (P-B) ratio, which is discussed in more detail below.
Metals can be classified into two categories: those that form protective oxides, and those that cannot. The protectiveness of the oxide can be attributed to the volume of the formed oxide in comparison to the volume of the metal used to produce this oxide in a corrosion process in dry air. The oxide layer can be unprotective if the ratio is less than unity because the film that forms on the metal surface is porous and/or cracked. Conversely, the metals with the ratio higher than 1 tend to be protective because they form an effective barrier that prevents the oxidizers from further reaction with the metal since the volume change is close to parity with underlying molecular structure.
P-B ratio can be defined as:
Where:
RPB—Pilling-Bedworth ratio
M—atomic or molecular mass
n—# metal atoms per molecule of the oxide
ρ—density
V—molar volume
The following connection can be shown based on the P-B ratio:
However, the exceptions to the above P-B ratio rules are numerous due to its generality. Many of the exceptions can be attributed to the mechanism of the oxide growth: the underlying assumption in the P-B ratio is that oxygen needs to diffuse through the oxide layer to the metal surface; in reality, it is often the metal ion that diffuses to the air-oxide interface. This philosophy, however, is specifically applied to dry conditions, not aqueous ones. A similar rationale can be applied to aqueous passivation films with, for example, greater consideration for hydroxide corrosion products.
The diffusion of ions to the anode or sometimes referred to as the anolyte will determine the current response. For aqueous electrochemical reactions, this can be predicted by the Cottrell equation. The Cottrell equation is defined for planar electrodes, but can also be derived for other geometries with corresponding Laplace operator and boundary conditions in conjunction with Fick's 2nd law of diffusion. In practice the constants of this equation can be simplified into one written as i=kt−1/2 where i is current density, t is time in seconds, and k is product of aforementioned constants.
Exceptions to the Pilling-Bedworth ratio are often due to the differing growth mechanisms and the location where volume change occurs (such an example of growth over time is illustrated in
The electrical component 110 (shown in
The Gibbs free energy (e.g., free enthalpy) is a metric which can indicate the maximum amount of energy in a chemical reaction within the electrical component 110. A quantitative measure of the favorability of a given reaction at constant temperature and pressure is the change AG in Gibbs free energy that is (or would be) caused by the reaction where ΔG=ΔH−T·ΔS, the difference between change in enthalpy H and product of temperature T and change in entropy S. In electrochemical reactions, ΔG=−nFE where n is electrons/mole, F is Faraday constant, and E is electrical potential. The value for E is the bias voltage and the driving force for electrochemical reactions. When ΔG for reaction is negative, it is an exergonic reaction or in other words, it will be more likely to react spontaneously or more favorable because there is a large driving force to lower the energy state of reactants. The reaction will proceed toward equilibrium where the ΔG=0. Generally, an exergonic reaction will also be exothermic. This means it will also have a negative ΔH which indicates heat from the reaction will be transferred to the environment. A large negative value for ΔH will have capacity to release more heat upon reaction. Heat energy of formation is associated with the products formed.
The kinetics of the reaction or essentially the reaction rate will determine the quantity of reaction products formed over time within the electrical component 110. This is a second critical factor in determining how much heat will be generated during reaction. Therefore, it is a function of the heat released per mole and the number of moles reacted. Heat will also be lost to the environment during this time, but when heat is quickly generated in confined areas with poor heat transfer, there will be an accumulation of heat energy that will contribute to a rise in temperature and ultimately degradation of materials. This can cause significant problems which could otherwise be avoided with better material selections. Specifically, a corrosion resistant set of metals included in the electrical component 110 that generates less heat from reaction will help address fundamental issues that can lead to degradation or failure.
The Standard Gibbs free energy of formation for metal oxidation products can be represented within an Ellingham diagram (not shown). Such diagrams can be used in prediction of the corrosion product energy per mole in the electrical component 110. For example, the Ellingham diagram specifically depicts the reaction of specific metals to metal oxides. Although, corrosion of metal leads to metal cations as well as multitude of products of oxidized products. For instance, metal complexes like metal hydroxide and oxyhydroxide and other complex metal coordination will result with varying enthalpies during passivation. The sum of energy released should be minimized to generate less heat. This generally refers to reactions which have ΔG closer to 0 J or lowest possible negative value. Note that the Ellingham diagram can illustrate metal oxide products at varying temperature or pressure, not under voltage bias. Prediction of products under bias was previously discussed above on active-passive transition.
In some exceptions, it may be favorable to use metals in the electrical component 110 which have more negative ΔG if they form strong bond with oxygen that leads to stable passivation film. The heat energy generated per mole of metal will depend on the metals used. However, rates of reactions and the rate of corrosion are also an important factor in minimizing heat energy. The kinetics are typically determined by experiment, but like all chemical processes, the kinetics in corrosion obey the Arrhenius relationship:
where R is the gas constant, k is the rate of reaction and k0 is the rate constant.
The areal current density (rate) of reduction can, or in some cases must, exceed the critical current density for passivation to ensure low corrosion rate in the passive state. The total heat formed from corrosion is a function of the heat generated per mole and the rate of the reaction. The product from the number of moles of corrosion produced and the energy per mole is equal to the heat input. In equation form,
produced. When the reaction occurs rapidly and energy cannot be easily dissipated to the environment during this time or the Heat Energy OUT or lost to its surroundings is minimized, the accumulation of heat energy will result in an increased temperature of the device. If the reaction rate can be slowed down, then the heat generated will have time to be transferred away from the electrical device 100 and Heat Energy OUT is maximized. This can be much safer and more ideal for operation in wet aqueous environments.
Below illustrates an equation for desirable heat generation within the electrical component 110:
In some implementations, heat can accumulate especially if localized within the electrical component 110. This type of heat accumulation can drive a corrosion kinetics faster within the electrical component 110 to cause rapid temperature increase of 100. For example, battery cells connected to 110 can be heated to an unacceptable threshold temperature. After a short duration at threshold temperature, they will experience thermal run-away and sometimes catastrophic failure. Below are heat examples related to various devices.
If, for example, a battery pack has a 70° C. (343 K) temperature limit for normal operation before “cut-off” where the pack is disabled and the acceptable limit for cells in the pack is 90° C. (363 K), then a 20 K=ΔT is acceptable change in temperature allowed from saltwater induced heating effects. In this simplified scenario, the battery pack weighs 1000 g and has a specific heat capacity of
and 50 g of salt water with specific heat capacity of
infiltrate the pack and short biased connectors made of steel where electro-chemical reactions occur rapidly and almost no heat (≈0 J) is dissipated from the pack. Therefore, the acceptable added Heat IN from salt water reactions can be found by the following estimations:
The allowable heat generation (ΔH) from salt water induced reactions is 24 kJ of heat released. If it is assumed that half or 50% of the heat energy is generated from steel corrosion, then the amount of steel that can be corroded during reaction can be estimated.
ΔHreaction=ΔHproducts−ΔHreactants=−822 kJ/mol
If maximum ΔH=−12 kJ, then 0.0146 moles of product can be formed. If there are 2 moles Fe per Fe2O3, then 0.0292 moles Fe can be reacted before reaching 90° C. The molecular weight for Fe is 56 g/mole, so 1.63 g of Fe can be reacted before leading to fire or explosion of, for example, a battery pack. If each strap weighs 0.55 g, then corrosion of just 3 straps could lead to catastrophic failure. This assumes the heat contribution from corrosion product is 50% input, when in practice it may be much less.
If an electrical connector in power tool has a 105° C. (378 K) temperature limit where glass transition occurs and the acceptable operating limit for tool is 55° C. (328 K), then a 50 K=ΔT is acceptable change in temperature allowed from saltwater induced heating effects. In this simplified scenario, the electrical connecter weighs 0.72 g and has a specific heat capacity of
and 2.2 g of salt water with specific heat capacity of
infiltrate the connector and short biased metals where electro-chemical reactions occur rapidly and almost no heat≈0 J is dissipated before failure. Therefore, the acceptable added Heat IN from salt water reactions can be found by the following estimates:
If a cell phone has a 120° C. (393 K) temperature limit where the electronic components may suffer irreversible degradation leading to failure and the acceptable operating limit for the phone is 70° C. (343 K), then 50 K=ΔT is acceptable change in temperature allowed from saltwater induced heating effects in case of water ingress. In this simplified scenario, the phone connecter weighs 80 g and has a specific heat capacity of
and 5 g of salt water with specific heat capacity of
infiltrate the phone and short biased metals where electro-chemical reactions occur rapidly and almost no heat (≈0 J) is dissipated before failure. Therefore, the acceptable Heat IN from salt water reactions can be found by the following estimates:
The electrical component 110 (shown in
A reaction will occur much more easily when appropriate catalyst is present because the overall activation energy for the reactions is lower. This is a result of a more favorable pathway for the reaction mechanism on the catalyst. In the case of inhibiting electrolysis, it is better to have a higher activation energy for the reaction (i.e. poor catalyst). Essentially this will raise the energy required for the reaction to proceed. In electrochemical reactions this is often referred to as the overpotential η and is equal to the difference in applied bias potential and the potential or voltage where the reaction will proceed (this can be predicted by the Nernst equation).
Similar to corrosion, thermodynamic and kinetic considerations exist for electrolysis reactions. The kinetic relationships for electrochemical reactions are described by the Butler-Volmer equation. However, at high overpotentials such as those which might be found in the active corrosion region of biased electrical connectors of power tools (e.g., electrical device 100), the equation can often be reduced to Tafel behavior. In short, the kinetics can be related to voltage at overpotentials where the current is a logarithmic function of the exchange current density on the metal (e.g., electrical component 110). A lower exchange current density effectively slows down the reaction rate and limits how much current can flow. The exchange current density is a function of the metal or alloy chosen for electrical connectors. Therefore, the heat energy can be reduced (e.g., minimized) by the metal chosen.
The table below illustrates exchange current density for hydrogen redox reactions in an acid electrolyte. Metals toward the top of chart would be more favorable for inclusion in the electrical component 110 because they can be reaction inhibitors.
i is the current density (A/cm2)
i0 is the exchange current density (A/cm2)
η is the overpotential (EBias−Ecorrosion or EBias−Etranspassive)
where
and k is Boltzmann's constant, T in Kelvin, e is electron charge, and α is the charge transfer coefficient.
As shown in
Catalyst behavior can be predicted in part by the fundamental physical principles of molecular surface interactions. In the case of hydrogen in acidic medium shown in
As shown in
The test configuration shown in
As shown in
Referring back to
As a second defining factor in the electrical component 110, the free energy of formation AG for corrosion products can be maintained at a minimum. Corrosion is an exothermic reaction which forms an oxidation product and releases heat. A choice of metals which releases a minimal amount of heat can be preferred in some implementations. In some implementations, this can be visualized from, for example, an Ellingham diagram. For instance, at 0° C., Copper can release approximately 300 kJ/mol from Cu to Cu2O while Aluminum can release approximately 1050 kJ/mol from Al to Al2O3 (e.g., a 3.5× greater amount of energy per mole than copper).
As an example, in battery terminal connectors, which were exposed to saltwater under 20V bias condition, the brass alloy can be desirable. A stable passivation layer can be formed on the anode (e.g., which can be a light red or green color depending on the alloy). A tin plated metal (e.g., steel) anode may not be desirable due to excessive heat generation. The anode metal can be completely oxidized in just a few minutes.
The electrical component 110 can be, or can include, an electrolysis resistant metal. Electrolysis includes at least two half reactions which occur at each respective electrode. An example electrolysis cell is shown in
Cathode (−) Half Reactions:
Na++e−→Na E° red=−2.71 V
2H2O+2e−→H2+2OH− E° red=−0.83 V
Anode (+) Half Reactions:
2Cl−→Cl2+2e− E° ox=−1.36 V
2H2O→O2+4H++4e− E° ox=−1.23 V
Electrolysis Reaction (Applicable)
2NaCl(aq)+2H2O→2Na+(aq)+2OH−(aq)+H2(gas)+Cl2(gas)
The electrical component 110 can be pre-passivated with the protective layer 120. The protective layer 120 can be a protective chemically-bonded coating. As mentioned above, the electrochemical reactions in saltwater are a function in part of the electrode geometry. Therefore, surface area of the corroding component will be an important factor in the rate of reactions. Minimizing reactive surface area is a key to controlling the electrochemical reactions. To minimize the reactive surfaces, smaller connectors can be used as the electrical component 110 or the non-contact area of the electrical component 110 can be covered with protective coatings such as the protective layer 120. This coating could be of varying chemical nature, but it should serve the function of a high dielectric film that resists breakdown under anticipated bias conditions in saltwater. Examples of this coating could include polymer films, plated metals, or pre-anodized surfaces. Their function is to inhibit corrosion and other electrochemical reactions.
In electrolysis or corrosion, reduction occurs at the lowest potential voltage or cathode. The overall reaction rate is strongly correlated to the cathode surface area. By covering the surfaces of this electrode, it will prevent electrolyte interaction and reduce reaction rates. The coating will also be more apt to maintain its stability in these reactions and thus be more favorable to cover (e.g. with a polymer or dielectric). Conversely, anode coatings will be more likely to be degraded by reactions. This applies to all coating examples listed previously. Therefore, identifying problem points for coating will be beneficial for safety, but also prevent unnecessary use of coatings (to save cost) in areas that are not problematic. Coatings can be processed to selectively coat the non-contact surfaces for electronic connectors.
In some implementations, due to incompatible coatings of electrodes (or metals which will effectively become electrodes in saltwater), there will be a need to coat some existing metals with corrosion and electrolysis resistant metals (e.g., protective layer 120) that are also compatible with connecting materials. Some metals may not be switched due to their inherent properties, cost, or other value. This could require them, To be plated. Electroplating is an example of this technique which can be used to apply electrochemical resistant coating. Furthermore, a metal selected for its low heat generation property may have a high galvanic junction potential (≳150 mV) relative to the connector and lead to galvanic corrosion when exposed to water. Therefore, plating of a compatible metal can serve several functions that minimize its reactivity.
As a specific example, in a battery pack, the casing material or terminals may be made of a metal which under bias is not suitable for a saltwater environment. In this instance, the casing may need to be plated to be suitable for corrosion resistance.
As another specific example, in a battery pack, the terminal material may be made of a metal of which is not suitable for a saltwater environment and the soldered connection is made of a different metal alloy which cannot be changed. They will form a galvanic junction potential when joined in electrolyte. The terminal material can be plated with a corrosion resistant coating that is ≲150 mV difference from the solder to reduce (e.g., minimize) galvanic corrosion.
Reducing surface area and increasing distance between biased components can slow reaction rates and the resultant heating of battery packs, for example. The electrode area and/or the electrolyte resistance can be contributing factors to, for example, the reactions rates.
In some implementations, a device can include a circuit where an electrical component in the presence of a voltage bias higher than a corrosion voltage of a base material (e.g., base metal) does not exceed breakdown potential. In some implementations, a device can include a circuit where a passivation potential of an electrical component is made of a material (e.g., metal) of stable passivation region that does not exceed breakdown potential.
In some implementations, a device can include a circuit where a voltage bias is present. This circuit can include a material made of a corrosion resistant material (e.g., metal) to saltwater or water with ions dissolved in it.
The device can be a battery comprising a plurality of battery cells and a set of straps, wherein a subset of the straps couple a terminal of a first battery cell to a terminal of a second battery cell, where the straps of the subset of straps are made of a corrosion resistant material with stable passivation to an expected bias potential. The device can be a power tool where the terminals within the power tool are made of a corrosion resistant material up to the bias voltage. The power tool terminal can be made of silver, brass, bronze, or other corrosion resistant copper alloy (such as a brass or bronze).
In some implementations, a battery cell can include a cell housing (e.g., can) and terminals that are made of a material (e.g., metal) exhibiting a higher breakdown potential (versus traditional steel or nickel plated metals). In some implementations, a device can include a circuit where only the anodes (high V) of the corrosion circuit are made with a highly corrosion resistant material. In some implementations, corrosion resistance of the high voltage (anodic) metals of a device can slow discharge of a battery to acceptable and/or safe rates. In some implementations, a device can include one or more materials (e.g., metals) that have free energy of formation (ΔG) for corrosion products that will reduce (or prevent) excess heat during their oxidation, avoiding thermal runaway in, for example, equipment, power tools, or battery packs. In some implementations, a device can be configured where the electrical connectors are designed to minimize corrosion reactive surface area (low area to volume ratio). In some implementations, an electrical connector (e.g., electrical component) can have a relatively low area relative to a volume (3-D) and/or can have a low circumference (e.g., perimeter) relative to an area (2-D).
In some implementations, a device can be configured where the components (e.g., anode and cathode) are placed at greater distance or with a barrier (e.g., an electrolytic path barrier) between them to increase electrolyte diffusion path between biased components and increase an electrolyte resistance.
In some implementations, a device can include a circuit where the electrical components in the presence of a voltage bias higher than the electrolysis potential and are made of a material (e.g., metal) which permits (e.g., only permits) low current exchange density with the reactive surfaces. This can be facilitated by formation of a passivation layer.
In some implementations, a device can include a circuit where a voltage bias is present and the circuit for carrying current is made of an electrolysis resistant material (e.g., metal) to saltwater. In some implementations, a device can be a battery where the straps made of an electrolysis resistant material with stable passivation under the target (e.g., expected) bias potentials. In some implementations, a device can be a power tool where the terminals within the power tool are made of an electrolysis resistant material up to the bias voltage.
In some implementations, a power tool terminal can be made of brass, bronze, or other corrosion resistant copper (or silver) alloy. In some implementations, a battery cell can include a cell can and terminals that are made of a material (e.g., metal) exhibiting a lower exchange current density and Tafel slope (versus traditional steel or nickel plated metals).
In some implementations, a device can include a circuit where the anodes (high voltage) (e.g., only anodes) of the circuit are subject to fluid exposure (e.g., saltwater) and include connector metals made with an electrolysis resistant material. In some implementations, a device can include a circuit where the cathodes (low voltage) (e.g., only cathodes) of the circuit are subject to fluid exposure (e.g., saltwater) and include connector metals made with an electrolysis resistant material. In some implementations, a device can include different metals (materials) where the different metals are used for the anode and cathode.
In some implementations, a device can be configured so that electrolysis impedance of the biased metals will slow the discharge of a battery to acceptable and/or safe rates in saltwater (as compared to conventional steel or nickel selections). In some implementations, a device can include metals that prefer to form electrolysis products which are inherently safer and/or less toxic (e.g. O2 instead of Cl2) in nature. In some implementations, a device can include one or more electrical connectors designed to minimize electrolysis reactive surface areas (low area to volume ratio). In some implementations, a device can include one or more electrical components that are spaced at greater distance or with longer electrolyte pathway to increase resistance.
In some implementations, a device can include a protective coating of biased electrical connectors in circuits that can prevent saltwater electrochemical half-reactions. In some implementations, cathode (low voltage coatings) (e.g., only cathode) connections are coated to protect against electrochemical reactions. In some implementations, cathode coatings can be configured to lower the available surface area for electrochemical cathode half-reactions and the overall electrochemical reaction rates.
In some implementations, a coating can be applied to a connector in the circuit where the base metal (material) may not be changed for some pre-determined reason in order to limit electrochemical reactions (electrolysis & corrosion). In some implementations, a coating can be configured to prevent contact of saltwater electrolyte from biased connectors.
In some implementations, a device can include a circuit where the components in the presence of a voltage higher than the base materials corrosion voltage and/or passivation potential are plated with a material of higher corrosion potential and/or passivation potential. In some implementations, a device can include a circuit where a voltage bias is present. This circuit can include current carriers made of a corrosion capable material. The metals are plated by a metal that are more corrosion resistant than the base current carrying material.
In some implementations, a device can be a battery where the straps are plated by a corrosion resistant material (stable passivation). In some implementations, a device can be a power tool where the terminals within the power tool are plated with a corrosion resistant material. In some implementations, a power tool terminal can be plated in brass, bronze, copper alloy, or silver.
In some implementations, a device can include a circuit where the cathodes (e.g., only the cathodes) of the corrosion circuit are plated with an electrochemical reaction resistant material. In some implementations, device can include a circuit where the anodes (e.g., only the anodes) of the corrosion circuit are plated with a high corrosion resistant material.
In some implementations, a battery cell can be configured where the cell is plated by, or including exclusively, a material exhibiting a higher passivation layer breakdown potential versus the base material (e.g. nickel plated steel). For example, in some implementations, a battery can (which can include an anode and a cathode) material can be a metal such as brass (rather than a nickel plated steel material). In some implementations, a battery cell can be plated in brass, bronze, copper-zinc alloy, silver, or similar corrosion resistant metal. In some implementations, a battery cell can be configured so that an external portion of the cell is plated in brass and the internal portion of the cell is plated in nickel.
In some implementations, a battery cell can be configured where the bottom portion (e.g., only the bottom portion) of the cell (negative side) is plated by a low corrosion resistant material. In some implementations, a battery cell can be configured so that the positive cap (e.g., only a positive cap) is plated by a low corrosion resistant material. In some implementations, a battery cell can be configured so that the positive cap and bottom portion of the cell are plated by conductive but electrochemically resistant materials.
The electrical component 110 can include an indicator of corrosion. For example, if the electrical component 110 is made of a brass material and is used as a corrosion resistant battery strap, an indication of corrosion can be found by the formation of a passivation on the high voltage side of the electrical component 110. Brass alloys can turn a color such as green (Brass 230) or red (Brass 464) when they begin to oxidize. In contrast, a steel battery strap will turn black and/or just dissolve. This visual indicator can be an indicator of water contamination, transfer of liability for improper use of equipment, and so forth.
In at least one general aspect, an apparatus can include a first electrical contact point having at a first target voltage potential, and a second electrical contact point having at a second target voltage potential that is different from the first target voltage potential. That apparatus can include an electrical component coupled to at least the first contact point where the electrical component includes an active-passive material configured to form a protective layer in response to a voltage difference between the first target voltage potential and the second voltage target potential while in a fluid in communication with the electrical component and the second contact point. The apparatus can include any combination of the following features.
The fluid functions as an electrolyte. The active-passive material has a passivation voltage range in which the protective layer forms on the electric component at a pH Level of the fluid. The passivation voltage range can span the range of the voltage difference. The active-passive material has a passivation behavior spanning the range of voltage bias, and the passivation range is based on a passivation potential and a transpassive potential. The active-passive material includes a material that inhibits an electrochemical reaction. The active-passive material is a material that inhibits an electrochemical reaction. The first contact point is included in a first cell of a battery and the second contact point is included in a second cell of the battery. The active-passive material is a metallic alloy. The protective layer is chemically bonded to the electrical component. The formation of the protective layer has a low energy of formation with less than a critical (e.g., 10° C.) temperature change in the electrical component. The active-passive material includes at least one of copper-zinc alloy, brass, bronze, or silver.
In another general aspect, a method can include identifying a target bias voltage potential difference between a first electrical contact point and a second electrical contact point included in an electrical device where the target bias voltage potential difference is based on a difference between a first target voltage potential at the first electrical contact point and a second target voltage potential at the second electrical contact point. The method can include selecting an active-passive material having a passivation voltage range spanning the target bias potential range, and configured to be coupled to at least the first contact point and to be in fluid communication with the second contact point. The method can include any combination of the following features.
The selecting is based on the active-passive material being an electrolysis inhibitor. A protective layer forms on the active-passive material at a pH Level of the fluid. The selecting is based on the active-passive material having a low energy of formation of corrosion products.
When an element, such as a layer, a region, or a substrate, is referred to as being on, connected to, electrically connected to, coupled to, or electrically coupled to another element, it may be directly on, connected or coupled to the other element, or one or more intervening elements may be present. In contrast, when an element is referred to as being directly on, directly connected to or directly coupled to another element or layer, there are no intervening elements or layers present. Although the terms directly on, directly connected to, or directly coupled to may not be used throughout the detailed description, elements that are shown as being directly on, directly connected or directly coupled can be referred to as such. The claims of the application may be amended to recite exemplary relationships described in the specification or shown in the figures.
As used in this specification, a singular form may, unless definitely indicating a particular case in terms of the context, include a plural form. Spatially relative terms (e.g., over, above, upper, under, beneath, below, lower, and so forth) are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The relative terms above and below can, respectively, include vertically above and vertically below. The term adjacent can include laterally adjacent to or horizontally adjacent to.
While certain features of the described implementations have been illustrated as described herein, many modifications, substitutions, changes and equivalents will now occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the scope of the implementations. It should be understood that they have been presented by way of example only, not limitation, and various changes in form and details may be made. Any portion of the apparatus and/or methods described herein may be combined in any combination, except mutually exclusive combinations. The implementations described herein can include various combinations and/or sub-combinations of the functions, components and/or features of the different implementations described.
This application claims priority to and the benefit of U.S. Provisional Application No. 62/441,519, filed Jan. 2, 2017, entitled, “Electrical Components for Reducing Effects from Fluid Exposure and Voltage Bias”, which is incorporated herein by reference in its entirety.
Number | Date | Country | |
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62441519 | Jan 2017 | US |