Method for safe storage and transportation of galvanic cells and batteries and chemically active substances

Abstract

FIELD: transportation; storage of dangerous goods.SUBSTANCE: transportation of galvanic cells and batteries containing alkaline and alkaline earth metals (lithium, sodium, magnesium), prone to thermal runaway, combustion and explosion upon overheating, mechanical damage, electrochemical degradation and devices containing them, chemically active substances of the 4th hazard class according to the UN classification: solid flammable and spontaneously combustible materials (for example, lithium, sodium, metal hydrides), substances that release oxygen or other oxidizers upon decomposition (peroxides, nitrates, chlorates, hypochlorites). A method has been proposed that involves completely immersing the hazardous cargo in a liquid inert medium.EFFECT: providing comprehensive protection from external factors, increasing the level of safety for the storage and transportation of hazardous goods, reducing the weight of the packaging, increasing the useful load, allowing for the reuse of the inert environment, and automating the control of cargo parameters.1 cl, 3 dwg

Description

[0001] Field of technology to which the invention relates

[0002] The invention relates to the field of transportation and storage of dangerous goods, in particular:

[0003] • Galvanic cells and batteries containing alkaline and alkaline earth metals (lithium, sodium, magnesium), prone to thermal runaway, fire and explosion when overheated, mechanical damage, electrochemical degradation and devices containing them,

[0004] • Chemically active substances of the 4th hazard class according to the UN classification:

[0005] • solid flammable and spontaneously combustible materials (eg lithium, sodium, metal hydrides),

[0006] • substances that release oxygen or other oxidizing agents during decomposition (peroxides, nitrates, chlorates, hypochlorites).

[0007] The invention is intended for use in:

[0008] • Logistics (transportation of batteries for electric vehicles, portable electronics, storage and delivery to the disposal site of faulty batteries),

[0009] • Industrial storage (chemical reagent warehouses, cargo terminals),

[0010] • Commercial transportation of dangerous goods by all types of transport;

[0011] • Individual use for transporting portable devices with batteries (smartphones, tablets, mobile chargers, medical devices) in carry-on baggage, luggage and personal transport.

[0012] Technology Level

[0013] The following similar technical solutions are known:

[0014] 1. Package type P903 in accordance with the Agreement concerning the International Carriage of Dangerous Goods by Road (ECE / TRANS / 352), used for the transport of lithium-ion batteries.

[0015] Disadvantages:

[0016] • provides only basic protection against mechanical damage;

[0017] • does not prevent thermal runaway;

[0018] • does not protect against moisture and oxygen;

[0019] • Does not provide short circuit protection.

[0020] 2. Sealed packaging according to patent DE 102020101243 B3, containing absorbent and heat-insulating materials.

[0021] Disadvantages:

[0022] • provides passive thermal protection only;

[0023] • does not prevent thermal runaway;

[0024] • has excessive weight (the weight of the package exceeds the weight of the payload);

[0025] • does not provide active heat dissipation.

[0026] 3. Sealed packaging with inert gas (argon) according to GOST 17746-96, intended for transportation of titanium sponge.

[0027] Disadvantages:

[0028] • requires absolute tightness;

[0029] • has low heat dissipation efficiency;

[0030] • does not prevent thermal runaway;

[0031] • not applicable to substances that release oxidizing agents (peroxides, nitrates, etc.) during decomposition.

[0032] Common disadvantages of known solutions:

[0033] • lack of comprehensive protection against all major risk factors: moisture, oxygen, mechanical damage, thermal runaway and ignition;

[0034] • limited effectiveness when transporting particularly hazardous substances of class 4;

[0035] • either too much weight or not enough protection.

[0036] Disclosure of the essence of the invention

[0037] The technical problem solved by the invention: the lack of a reliable comprehensive solution for protecting dangerous goods (galvanic cells, batteries, devices containing them and chemically active substances of hazard class 4) from:

[0038] • environmental influences (oxygen, moisture),

[0039] • thermal runaway,

[0040] • ignition during storage and transportation.

[0041] The proposed solution includes:

[0042] 1. A method for the safe storage and transportation of dangerous goods, including:

[0043] • complete immersion of dangerous goods in a liquid inert medium based on an organofluorine compound selected from the group:

[0044] • perfluorocarbons (PFCs),

[0045] • fluoroketones (FC),

[0046] • perfluoroalkyl ethers (PFAE),

[0047] • perfluoropolyethers (PFPE),

[0048] • hydrofluoroolefins (HFO),

[0049] • criteria for selecting an inert environment:

[0050] • chemical compatibility with dangerous goods;

[0051] • boiling point below the flash point for substances belonging to hazard class 4,

[0052] • boiling point is below the thermal runaway temperature threshold for batteries,

[0053] • determination of the required and sufficient amount of inert medium liquid:

[0054] • The amount of heat that can be absorbed by an inert environment solely due to the heat of latent vaporization must not be less than the amount of heat that can be released by the dangerous goods during thermal runaway or exothermic chemical reactions,

[0055] • The heat capacity of the inert environment is not taken into account since the amount of heat absorbed by this mechanism depends on the ambient temperature and can change.

[0056] • Recycling of organofluorine compound.

[0057] • applying a barrier layer of organosilicon liquid over a neutral liquid.

[0058] This way, the stated technical problem is solved:

[0059] • Complete immersion of dangerous goods in a liquid inert medium:

[0060] ○ Displaces the adsorption layer of air gases and traces of water from the surface of an immersed solid body;

[0061] ○ Forms an impermeable barrier between a solid and the environment (air gases and water vapor);

[0062] • The use of an organofluorine compound in a liquid state of aggregation, selected according to the above criteria, when the temperature of the hazardous cargo increases (as a result of physical or chemical processes occurring in it with the release of heat) or the environment, a two-phase cooling mechanism is triggered:

[0063] ○ Heat absorption due to the heat capacity of the inert medium (the specific heat capacity of a liquid is several times higher than that of gases). The proportion of heat absorbed is -10%;

[0064] ○ Intensive heat absorption due to the latent heat of vaporization upon reaching the boiling point of the organofluorine compound (this heat absorption mechanism is absent in gases). The proportion of absorbed heat is ~90%;

[0065] As a result of intensive heat removal from the heat source, the temperature does not reach the thermal runaway threshold and ignition temperature, and exothermic reactions die out.

[0066] If, for any reason (extreme ambient temperature rise, current density of the battery accepted for transportation significantly higher than declared), the heat absorption capacity of the two-phase cooling mechanism is insufficient and the heat source temperature reaches ignition temperature or thermal runaway, the chemical flame inhibition mechanism, which is possessed by organofluorine substances, is activated. This mechanism is based on the chemical neutralization of flame radicals, with the effect achieved in a fraction of a second.

[0067] 2. Device for implementing the method:

[0068] 1. Main components:

[0069] • Main packaging:

[0070] ○ Contains inert liquid, dangerous goods;

[0071] ○ The shape and size of the packaging ensure:

[0072] - the minimum distance from any internal surface of the packaging to the surface of the cargo placed in it is not less than 5 mm

[0073] - the possibility of complete immersion of the load in an inert liquid;

[0074] - the packaging must be filled to no more than 95% of its internal volume;

[0075] ○ Packing material:

[0076] - chemically compatible with hazardous cargo and inert environment substance (does not enter into chemical reaction, does not dissolve and does not dissolve itself),

[0077] - can be hard and provide shockproof protection or elastic,

[0078] - contains a device for draining and filling inert liquid with an overflow protection function,

[0079] ○ contains a liquid level sensor with indication of the minimum and maximum liquid level, it can be made non-hermetic, in this case:

[0080] - equipped with a device or have a shape that prevents overflow and splashing,

[0081] - equipped with a device (optional) for applying a protective layer of organosilicon compound (polymethylxyloxane) to the surface of an inert liquid to reduce its evaporation.

[0082] ○ can be made sealed, in which case it is equipped with:

[0083] - a pressure equalization valve that ensures the pressure inside the package is within a specified range in relation to the ambient pressure,

[0084] - with a lid and a locking mechanism.

[0085] 1. Additional elements:

[0086] ○ Outer rigid packaging containing one or more main packaging;

[0087] ○ The outer packaging can be equipped with a cooling system and thermal insulation for storing and transporting flammable substances in high temperature environments;

[0088] ○ Inert liquid filling / drainage system with condensation and filtration;

[0089] ○ Monitoring system: GSM / GPS, temperature, liquid level, shock, vibration sensors;

[0090] ○ Means for securing cargo inside the packaging;

[0091] ○ Shock absorbing elements in outer packaging;

[0092] ○ Inert liquid regeneration device.

[0093] ○ Inert liquid reserve tank to maintain the inert liquid level in the main package.

[0094] Technical result:

[0095] 1. Comprehensive protection against all key risk factors.

[0096] 2. Reduction in packaging weight by 30-50% compared to gas-filled analogues.

[0097] 3. The inert medium can be reused multiple times after regeneration.

[0098] 4. Universal application for various types of transport.

[0099] Brief description of drawings:

[0100] Fig. 1. Layout of dangerous goods in the main packaging;

[0101] Fig. 2. Diagram of the placement of dangerous goods in the main packaging equipped with an additional outer rigid packaging;

[0102] Fig. 3. Layout of several pieces of dangerous goods in additional outer rigid packaging;

[0103] Implementation of the invention:

[0104] 1. Device design options:

[0105] 1. Compact (for mobile power sources, smartphones, tablets, medical devices containing galvanic cells and batteries for transportation in hand luggage, baggage and personal transport) (Fig. 1) contains a sealed main package (1) with a volume of up to 1 liter made of impact-resistant material and equipped with:

[0106] - transparent walls for visual control (optional),

[0107] - liquid level indicator and overheat protection system activation (optional);

[0108] - sealed lid with a locking device;

[0109] - safety valve;

[0110] The battery (2) is placed in the main packaging and fixed in such a way that there is a gap of at least 5 mm between the battery case and the inner walls of the packaging, an inert liquid consisting of an organofluorine compound (3) is poured in such a way that the battery is completely immersed in the inert liquid and the total volume of the battery and inert liquid is no more than 95% of the internal volume of the packaging.

[0111] 2. Logistics (Fig. 2) (for storage and transportation of batteries for production needs, collection and removal for disposal of faulty batteries, transportation of small quantities of substances of hazard class 4 - laboratory samples) contains a sealed or open-top main packaging (1) made of an elastic chemically resistant material, in which the battery is placed (2) and filled with an inert liquid consisting of an organofluorine compound (3). Additionally, a layer of non-volatile organosilicon liquid (4) is applied on top of the inert liquid in order to reduce evaporation of the organofluorine compound, so that the organosilicon liquid completely covers the surface of the inert liquid with a layer at least 5 mm thick.The dimensions and shape of the primary packaging are determined based on the following basic requirements: the volume of liquid and solid contents must not exceed 95% of the internal volume of the packaging, with batteries or other hazardous cargo completely covered by a layer of inert liquid. Furthermore, in the case of an open container, the packaging design and liquid level must be such as to prevent spillage of the liquid component during normal handling. The primary packaging is placed within a rigid, impact-resistant outer packaging (5). The space between the primary packaging and the outer rigid packaging is filled with a shock-absorbing, non-flammable material (6), which simultaneously serves as a securing element for the primary packaging and as an absorbent material to absorb the liquid phase of the primary packaging's contents in the event of damage and spillage.Such materials may include, but are not limited to, foam glass, expanded clay, expanded vermiculite, perlite, granulated basalt wool, and others. Additionally, the packaging may be optionally supplemented with the following elements:

[0112] - Monitoring system: GSM / GPS;

[0113] - Temperature, pressure, liquid level, shock, vibration sensors;

[0114] - Device for separate filling, draining and replenishing of inert liquid and organosilicon liquid during storage and transportation;

[0115] 3. Commercial (commercial cargo transportation) (Fig. 3):

[0116] - The outer packaging (5) is made in the form of a standardized shipping container (railway container, sea container, air container, etc.), which contains several main packages (1) containing batteries (2) and filled with inert liquid (3) and organosilicon liquid (4),

[0117] - Main packaging is securely fastened to prevent shifting within the container. The fastening system is designed for each container type and transport conditions.

[0118] - The container can be equipped with a monitoring system: GSM / GPS, pressure sensors, leaks (optional),

[0119] - The container can be equipped with a forced cooling system and thermal insulation for the transportation of flammable substances and in high ambient temperature conditions.

[0120] - The container can be equipped with a reserve tank for automatic or manual replenishment of the inert liquid level in the main packages based on the readings of the monitoring system.

[0121] - The container can be equipped with an inert liquid regeneration device (can be combined with a reserve tank).

[0122] 4. Open container (for temporary storage of faulty batteries to assess their stability and the possibility of transportation for disposal, conducting experiments on the compatibility of inert liquid with various materials, and other purposes). 2. General sequence of actions:

[0123] 1. Selection of inert medium and calculation of its quantity:

[0124] - The inert environment should not react with the packaging material and the cargo placed in it;

[0125] - The boiling point of the inert liquid must not exceed the cargo's ignition temperature or thermal runaway threshold. Ambient temperature conditions must also be taken into account. In the event of high ambient temperatures (especially during periods of intense solar activity), which could cause significant heating of the packaging and inert liquid, it is recommended to increase the margin of difference between the liquid's boiling point and ignition temperature to 10-20 degrees. If this difference cannot be achieved, it is recommended to use outer packaging equipped with thermal insulation and an active cooling system.

[0126] - The amount of inert liquid is determined based on the amount of heat it can absorb due to the latent heat of vaporization (calculated according to the manufacturer's data). It must be 10% greater than the amount of heat that the hazardous cargo could potentially release during ignition or thermal runaway (calculated according to the manufacturer's data or, if unavailable, based on test results). When transporting known defective batteries and devices containing them, or substandard Class 4 hazard substances (e.g., those with increased moisture content), it is recommended to increase the amount of inert liquid by 25% and equip the device with a reserve tank for replenishing the inert liquid level during transport.

[0127] 2. Determining the size and shape of the main packaging:

[0128] - Volume of the main packaging: the sum of the volume of the cargo, inert environment, as well as sensors and other devices placed in the inner packaging should not exceed 95% of the internal volume of the main packaging. This is necessary to compensate for thermal expansion.

[0129] - The packaging shape must ensure that the dangerous goods are completely immersed in an inert liquid during transport or storage. The inert liquid layer above the top of the dangerous goods must be at least 5 mm thick. The safety valve must be located above the inert liquid level. If the packaging does not have a clearly defined transport position (storage position), this requirement must be met for any possible position of the packaging in space.

[0130] 3. Selection and marking of outer packaging:

[0131] - The selection and marking of containers depends on the nature and nomenclature of the cargo and the mode of transport in each specific case and is carried out in accordance with applicable international and national regulations governing the transport of dangerous goods. For example, the transport of dangerous goods by air is regulated by the "Technical Instructions for the Safe Transport of Dangerous Goods by Air" (ICAO Doc 9284). Similar documents have been issued for land, sea, and river transport at both the international and national levels;

[0132] 4. Features of packaging, transportation, storage and unpacking: This section only specifies the features of the packaging procedure specific to this invention; all other procedures prescribed by the relevant regulatory documents are not specified here, but must be strictly followed.

[0133] - The order of placement of cargo and inert medium:

[0134] • The load is placed and secured in a dry and clean main packaging,

[0135] • Inert liquid is poured in a volume determined by calculation, but not less than is necessary to fulfill the condition of complete immersion of the dangerous cargo in an inert environment.

[0136] - Transportation or storage is carried out in accordance with established regulations. If the package is equipped with a condition and location monitoring system (usually advisable when transporting cargo that poses a high risk, such as damaged batteries or galvanic cells with a high charge density, or in accordance with the terms of the issued transportation permit), the cargo's condition is monitored.

[0137] - Unpacking (Recommended procedures to reduce inert liquid consumption):

[0138] • The inert liquid is drained through the drain and fill device into a container specially designed for this purpose,

[0139] • The packaging is kept in a closed state for at least 10 minutes to drain the remaining inert liquid from the surface of the cargo,

[0140] • The remaining liquid is drained, air is blown to remove and collect the vapors of the inert liquid,

[0141] • The lid opens and the load is removed.

[0142] - Regeneration of inert liquid to remove mechanical impurities and dissolved gases:

[0143] • Filtration (can be performed during draining),

[0144] • Removal of dissolved gases is achieved by stirring, which can be combined with heating.

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