CN103563159A - Electrochemical cell - Google Patents

Electrochemical cell Download PDF

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Publication number
CN103563159A
CN103563159A CN201280025822.4A CN201280025822A CN103563159A CN 103563159 A CN103563159 A CN 103563159A CN 201280025822 A CN201280025822 A CN 201280025822A CN 103563159 A CN103563159 A CN 103563159A
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Prior art keywords
protection equipment
single cell
sei layer
stabilization additives
lithium
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蒂姆·谢弗
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LI TEC VERMOEGENSVERWALTUNGS GmbH
Li Tec Battery GmbH
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LI TEC VERMOEGENSVERWALTUNGS GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Electrochemical cell having at least one negative electrode, at least one positive electrode and at least one electrolyte, wherein the at least one negative electrode essentially has at least one carbon-containing electrochemical active material which is capable of forming a ''solid electrolyte interface'', that is to say an SEI layer, on at least parts of the surface of the electrode, the electrochemical cell has at least one stabilizing additive which is capable of stabilizing the SEI layer, wherein at least one protective device is provided in the electrochemical cell, said protective device having the at least one stabilizing additive and preferably being designed as a storage container, wherein the at least one stabilizing additive is at least partially released from the at least one protective device when, in respect of the SEI layer, at least one predetermined parameter is reached or exceeded or undershot.

Description

Electrochemistry single cell
The full content of priority application DE 10 2,011 102 628 becomes the application's a part by reference.
The present invention relates to a kind of electrochemistry single cell, wherein this electrochemistry single cell has at least one stabilization additives.This additive can make the SEI layer (SEI=Solid electrolyte interface solid electrolyte interface) of electrode stable.This stabilization additives as required protected equipment (being particularly designed to hold-up vessel) discharges.Monocell preferably can be for electric motor driven, preferably with hybrid power, drive or with the vehicles of " plug-in type " work.
Electrochemistry single cell, particularly lithium-secondary cell, because its high-energy-density and high power capacity are applied to mobile information apparatus as accumulator, for example mobile phone, instrument or electric automobile and the automobile that drives with hybrid power.Although these electrochemistry single cell applications are very different, but all monocells that are used (especially for the monocell that drives automobile) must meet high requirement: in the situation that weight is as far as possible little, have high as far as possible capacitance and energy density, it keeps stable about high quantity charging and discharging circulation.
The durability of electrochemistry single cell often depends on the aging of electrode just.In ageing process, electrochemistry single cell is lost capacity and electric power.This process occurs more or less in mostly conventional electrochemistry single cell, and depends on environment for use (temperature, storage condition, charged state etc.), but also depends on quality and the processing of material during electrochemistry single cell manufacture process.Therefore, the pure material of high-quality processing can cause durable electrochemistry single cell, and it is also only less aging through the long term, less loses in other words capacity and electric power.
Yet these measures are usually not enough to obtain durable electrochemistry single cell, because there is chemical reaction at monocell duration of work in monocell inside, this reactive moieties ground is irreversible, and it can cause the capacitance loss of electrochemistry single cell.
Example about this chemical reaction is to form so-called SEI layer.SEI layer (SEI=Solid electrolyte interface solid electrolyte interface) is on the active material and the critical surface between nonaqueous electrolyte of negative electrode and/or anode, in first charging and discharging cycle period, form, and substantially by the product of electrolyte and active material, formed.These product can be for example Li 2o, LiF, macromolecular compound or (partly) carbonate is Li for example 2cO 3.The formation for the first time of SEI layer causes the capacitance loss of initial irreversible electrochemistry single cell.
Especially, in this electrochemistry single cell, wherein the electrochemical active material of negative electrode has in fact the material of carbon containing, forms stable SEI layer marginal to the durability of monocell on the surface of electrochemical active material.The product of mentioning before some, for example (partly) carbonate is metastable compound, its under certain conditions (for example, under high temperature) can resolve into stable product, for example LiF.In this case, can occur crackle in SEI layer inside, electrolysis mass-energy is thus infiltrated in (einringen) active material again in a large number, and described product further decomposes, and this may further cause the irreversible capacitance loss of monocell; SEI layer increases.
When overcharge monocell, may cause process in contrast, SEI layer decomposes.In both cases, the growth of SEI layer and resolution make monocell can suffer capacitance loss; In other words make monocell aging.
SEI layer not only all plays an important role for the aging of monocell but also for the safety of monocell, and this is by hindering Li dendrite to grow with it, or even the growth of prevention Li dendrite.Therefore, especially owing to occurring crackle in SEI layer inside, Li dendrite can pass described crackle or interstital growth, and this may cause monocell short circuit.
So, in order to keep stable as far as possible SEI layer, need to originally realize with not low one-tenth.In publication US 2009/0106970 A, a kind of method on six rank for the manufacture of having the lithium ion battery group of SEI layer has exemplarily been described.
So target of the present invention is to provide a kind of simple method for the manufacture of particularly durable electrochemistry single cell.
This is realized by the instruction according to independent claims of the present invention.The preferred embodiments of the present invention are themes of dependent claims.
This basic task is by having at least one negative electrode, at least one positive electrode and at least one electrolyte electrochemical monocell solve, wherein said at least one negative electrode has in fact the electrochemical active material of at least one carbon containing, this active material can form " solid electrolyte interface " layer at least part of surface of electrode, it is SEI layer, wherein electrochemistry single cell has at least one stabilization additives, this additive can be used in stablizes SEI layer, a protection equipment is wherein at least set in electrochemistry single cell, this protection equipment has at least one stabilization additives and is preferably designed to be hold-up vessel, while being wherein at or above or below at least one predetermined parameter about SEI layer, at least one stabilization additives is discharged from least one protection equipment at least in part.
According to the advantage of electrochemistry single cell of the present invention, be; by applying at least one protection equipment; at least one stabilization additives can only interact with SEI layer when needed; therefore and at electrochemistry single cell duration of work, can by less desirable chemistry and/or physical process, do not damaged as previous example, making unavailablely when needed maybe can not provide enough electric weight.
" in fact " meaning is, at least reaches 50%, at least reaches 75%, at least reaches 90%, at least reaches 99%, and preferably reaching 100% electrochemical active material is carbon containing.
In a preferred embodiment; electrochemistry single cell has at least one protection equipment; it has the first shape and the second shape, wherein when be at or above or below at least one the predetermined parameter (content of temperature, pressure, pH value, chemical compound (particularly HF, H particularly about SEI layer 2o, CO 2), the capacitance loss of monocell or the combination of voltage or these parameters) time, described at least one protection equipment, from the first change of shape to the second shape, wherein protects equipment to discharge aforesaid stabilization additives with the second shape.
In a preferred embodiment, electrochemistry single cell has at least one protection equipment, and it has at least one macromolecular material.
In a preferred embodiment, electrochemistry single cell has at least one protection equipment, and it is constituted as the hold-up vessel at least one stabilization additives.
In a preferred embodiment, electrochemistry single cell has at least one stabilization additives, it is from phenylene carbonic ester (Phenylencarbonat), sub-vinyl carbonate (Vinylidencarbonat), fluorine-containing or not fluorine-containing organic boronic lithium, difluoro (oxalate closes) lithium borate (LiDFOB) or two (oxalate closes) lithium borate (LiBOB) and fluorine-containing or not fluorine-containing organic phosphoric acid lithium, tetrafluoro (oxalate closes) lithium phosphate (LiTFOP), three (oxalate closes) lithium phosphate (LiTOP), or compound dynamics and/or thermodynamically stable electric insulation and/or ionic conduction, dynamics and/or thermodynamically stable lithium salts, inorganic lithium salt, LiF, LiOH, Li 2cO 3and Li 2in O or its mixture, select.
In a preferred embodiment, electrochemistry single cell has negative electrode, and it has the electrochemical active material of at least one carbon containing, and this active material is selected from non-crystalline graphite, Scaly graphite, carbonaceous material or its mixture.
In a preferred embodiment, electrochemistry single cell has positive electrode, and it has at least one electrochemical active material at least in part, and this active material is from selecting with lower: at least one compound L iMPO 4the lithium metal oxide of the lithium metal oxide of (wherein M is the transition-metal cation that at least one selects from the combination of manganese, iron, cobalt, titanium or these elements) or at least one spinel-type or lithium metal mixing oxide (wherein metal is selected from cobalt, manganese or nickel) or at least one non-spinel-type or lithium metal mixing oxide (wherein metal is selected from cobalt, manganese or nickel) or its mixture.
sEI layer
According to the present invention, SEI layer is preferably being formed on during the first charge and discharge cycles on electrochemical active material surface at least in part, particularly, on the surface of the electrochemical active material of negative electrode, described negative electrode preferably has in fact the electrochemical active material of carbon containing.
The formation of SEI layer can realize with reacting of surface of active material by the electrolyte containing lithium ion.But also possible that, the formation of SEI layer for example, realizes by affecting the reaction of the additive (LiBOB) of SEI layer formation.
Preferably, reaching 40%, preferably reaching 70%, further preferably reaching on 100% electrochemical active material surface and form SEI layer.
Preferably, SEI layer have size from 0nm until 20nm, preferably until 30nm, preferably until 40nm, preferably until 50nm, further preferably until the average thickness of 60nm.
In a preferred embodiment, SEI layer has 30nm above and the average thickness below 50nm.
In a preferred embodiment, SEI layer has the attribute of electric insulation and lithium ion conduction.
Preferably, SEI layer has the compound in following group at least in part: inorganic lithium salt (particularly LiF, LiOH, Li 2o), (partly) carbonate (Li particularly 2cO 3, ROCO 2li(is R=alkyl, olefine, thiazolinyl or aromatic substituents wherein) and (CH 2oCO 2li) 2), macromolecular compound (for example polyolefin) or its mixture.
Term " stable " SEI layer is understood to, the average external volume of SEI layer changes, the rising that particularly average thickness during the average thickness of SEI layer and charge and discharge cycles is for the first time compared along with charge and discharge cycles quantity does not change or without obviously changing, does not for example become in other words thicker or thinner.In addition, " stable " SEI layer does not preferably have and can cause the surface of active material to be exposed to electrolytical crackle or pore.Stable SEI layer preferably has in fact dynamics and/or thermodynamically stable compound, preferably LiF, LiOH, Li 2cO 3and Li 2o or its mixture.
For the possible measurable parameter of stable SEI layer, it can be the constant volume of monocell for example.
Term " unsettled " SEI layer is understood to, the average change in volume of SEI layer, particularly the average thickness of SEI layer is compared with average volume, particularly with charge and discharge cycles for the first time during the rising compared along with charge and discharge cycles quantity of average thickness obviously change, for example become in other words thicker or thinner.When overcharging electrochemistry single cell, SEI layer is for example decomposed.Further, unsettled SEI layer can have and can cause surface of active material to be exposed to electrolytical crackle or pore.Unsettled SEI layer has metastable compound, for example ROCO at least in part 2li or (CH 2oCO 2li) 2, it is for example broken down into stable compound under certain condition when improving temperature, can produce aforesaid crackle or pore thus.Further, unsettled SEI layer is unable to bear or can not withstands with enough degree increasing of Li dendrite.
" stereomutation " is understood to the change of the expansion of SEI layer in all degrees of freedom.
SEI layer " become unstable " or " being unsettled " according to embodiment by electrochemistry single cell inside, about SEI layer, be at or above or below at least one predetermined parameter and define.This predetermined parameter preferably can be selected from following group: specific temperature, specific temperature range, specific pressure, specific pressure limit, specific pH value, specific pH value scope, specifically SEI layer stereomutation amount, specific chemical compound (for example HF, H 2o, CO 2) content, specific monocell capacitance loss, specific voltage, specific voltage range or its combination.
For possible measurable parameter of unsettled SEI layer, it can be the irreversible capacity loss of monocell for example.
stabilization additives
Term " stabilization additives " is understood to according to the present invention can be used in to be stablized SEI layer and/or self can be used in all, the additive known to the skilled substantially that forms stable SEI layer.According to prior art, this stabilization additives is before manufacturing electrochemistry single cell or be added into electrolyte simultaneously.In other words,, when SEI layer is when first charging and discharging cycle period was formed completely, these additives exist.
In one embodiment, at least one stabilization additives is preferably selected from following group: phenylene carbonic ester, sub-vinyl carbonate, fluorine-containing or not fluorine-containing organic boronic lithium, for example difluoro (oxalate closes) lithium borate (LiDFOB) or two (oxalate closes) lithium borate (LiBOB) and fluorine-containing or not fluorine-containing organic phosphoric acid lithium, for example tetrafluoro (oxalate closes) lithium phosphate (LiTFOP) or three (oxalate closes) lithium phosphate (LiTOP) or its mixture.
In a preferred embodiment, at least one stabilization additives is selected from following group: the compound of dynamics and/or thermodynamically stable electric insulation and/or ionic conduction, preferably dynamics and/or thermodynamically stable lithium salts, preferably inorganic lithium salt, preferably LiF, LiOH, Li 2cO 3and Li 2o or its mixture.
Term " make SEI layer stable " is understood to, at least one stabilization additives interacts with SEI layer, and SEI layer at least in part, is preferably fully stablized thus, is particularly restored to its reset condition.
In a preferred embodiment, realize and stablizing, particularly recover SEI layer preferably by embedding and/or gather at least one stabilization additives in the defect of SEI layer.Preferably, described at least one stabilization additives has the attribute of electric insulation and/or ionic conduction, particularly lithium ion conduction.Preferably, described at least one stabilization additives is designed to be similar to, preferably be same as at least one and appear at the compound in SEI layer, preferably be similar to or be same as at least one and appear at thermodynamics in SEI layer and/or the compound of dynamic stabilization, preferably be designed at least one inorganic lithium salt, particularly LiF, Li 2cO 3or Li 2o.
The advantage of using at least one to be in fact originally present in stabilization additives in electrochemistry single cell or that form is therein that only marginally, preferably interference-free, affects chemistry and/or the physical process of in electrochemistry single cell, carrying out to this additive.
protection equipment
Term " protection equipment " is understood at least one equipment according to the present invention; it has at least one stabilization additives; the interaction of at least one stabilization additives and SEI layer is at least reduced, is preferably prevented from, until SEI layer is unsettled or becomes unstable.
Particularly advantageously, protection equipment designed to be used the hold-up vessel of at least one stabilization additives in one embodiment.
The advantage of this at least one protection equipment is; at least one stabilization additives can only interact with SEI layer when needed; therefore and at electrochemistry single cell duration of work, can by less desirable chemistry and/or physical process, do not damaged as previous example, making unavailablely when needed maybe can not provide enough electric weight.For being preferably unsettled when SEI layer or while becoming unstable, preferably when being at or above or below predetermined parameter about SEI layer at interactional needs between at least one stabilization additives and SEI layer.This predetermined parameter can preferably be selected according to the present invention from following group: specific temperature, specific temperature range, specific pressure, specific pressure limit, specific pH value, specific pH value scope, specifically SEI layer stereomutation amount, specific chemical compound (for example HF, H 2o, CO 2) content, specific monocell capacitance loss, specific voltage, specific voltage range or its combination.
At least one protection equipment preferably has the first shape or the second shape; wherein the difference of the first shape and the second shape is; the first shape reduces to minimum degree the interaction of at least one stabilization additives and SEI layer; preferably stop this interaction; and wherein the second shape makes the interaction of at least one stabilization additives and SEI layer become possibility, preferably strengthens this interaction.
At least one protection equipment preferably can be under certain condition when HF or water (for example higher pH value in electrolyte solution, or the temperature improving or have specific compound, for example) from the first change of shape to the second shape.
For example, according to mechanism like known class in drug research.Wherein micella capsule is formed, and pharmaceutically active substance is positioned at its inside.The micella capsule of " loading " is used in pointedly " supply " pharmaceutically active substance to target cell like this.In such cases, for example, while being placed in the target cell structure for example with receptor, micella capsule is " docking " on receptor, discharges thus its content.According to from the known idea of medicine practice, active ingredient (being similar to relevant stabilization additives here) can be postponed and/or can be released corresponding to certain physiological parameter, and this can be extended to electrochemistry single cell in principle.
In one embodiment, at least one protection equipment has at least one material at least in part, and this material can contribute to form the first shape and/or second shape of this at least one protection equipment.
" material " is understood at least one compound or at least one compound mixture.Described material for example can be comprised of one or more polymer.
Material must be selected, make in electrochemistry single cell normal work period not damaged, thereby stabilization additives is released.
Preferably, at least one material at least in part can be under certain condition for chemistry and/or physical reactions, and the change procedure of participation protective equipment the since first to second shape and/or make change procedure and/or support transfer process preferably thus.
At least one protection equipment preferably has at least one macromolecular material at least in part.
In one embodiment, protection equipment has the material that starts to melt and/or change its phase more than uniform temperature, preferably at least one macromolecular compound at least in part.
In one embodiment, at least one protection equipment has at least one material at least in part, and it can be used at least one chemical reaction.Described material preferably can react with at least one " less desirable " compound, and this compound produces when SEI layer becomes unstable, or participates in the destabilization of SEI layer.These " less desirable " compounds are for example acid, particularly Bronsted acid, preferably HF, CO 2, H 2o or its mixture.
Use can react with at least one " less desirable " compound that (this compound produces when SEI layer becomes unstable, the benefit of material or the destabilization of participation SEI layer) is, described compound is at least in part by chemical reaction " consumption ", particularly be decomposed, and therefore reduced it to electrochemistry single cell injurious effects, preferably suppressed this impact.In addition advantageously, at least one stabilization additives is only just released when there is at least one corresponding " less desirable " compound.
In a preferred embodiment, at least one protection equipment has a kind of material at least in part, and this material has at least one ester bond R 1-C (=O)-O-R 2.At this R 1and R 2can be identical or different.In this case, this compound preferably can (Bronsted acid HR particularly, it be preferably at least in part in dissociation form, particularly as H with water and/or acid +and R -) there is chemical reaction (particularly ester cracking), particularly producing corresponding alcohol roh and corresponding sour RCO 2under the condition of H, there is this chemical reaction.Preferably, protection equipment has polyester at least in part.
In a preferred embodiment, at least one protection equipment has a kind of material at least in part, and this material has at least one ehter bond (R 1-O-R 2, R 1and R 2can be identical or different), its can with water and/or acid (Bronsted acid HR particularly acid, it is preferably at least in part in dissociation form, particularly as H +and R acid -) there is chemical reaction (particularly ether-splitting solution), particularly producing corresponding ethanol R 1/2oH and R 1/2-R acidcondition under there is this chemical reaction.Preferably, protection equipment has polyethers at least in part.
In a preferred embodiment, at least one protection equipment has a kind of material at least in part, and this material has at least one disulfide bond R 1-S-S-R 2.At this R 1and R 2can be identical or different.This this compound preferably can, at reducing condition, issue biochemical reaction especially, particularly under the condition of the cracking of disulfide bond, (for example forming sulfydryl R 1/2under the condition of-SH) there is this chemical reaction.
In a preferred embodiment, at least one protection equipment has a kind of material at least in part, this material at least in part can with CO 2chemical combination.This can be preferably appearance by epoxide group or amine groups obtain.
In one embodiment, at least one protection equipment is formed and seals at least in part.
In another embodiment, at least one protection equipment is formed separating foil at least in part.
At least one stabilization additives that at least one protection equipment has is preferably disposed in electrochemistry single cell inside.
In one embodiment, at least one the protection equipment that has at least one stabilization additives is disposed in electrolyte at least in part.This preferably has by interpolation, and at least one protection equipment of described at least one stabilization additives occurs to electrolyte, and this additive is introduced in electrochemistry single cell subsequently.The advantage that had is like this, at least one the protection equipment with described at least one stabilization additives is dispensed on electrochemistry single cell inside substantially equably, and the electrochemical active material that is preferably dispensed on negative electrode is inner.At least one the protection equipment with at least one stabilization additives preferably has for several microns, several nanometers preferably, preferably be less than 100 μ m's, further preferably be less than 75 μ m's, further preferably be less than 50 μ m's, further preferably be less than 10 μ m's, further preferably be less than 500nm's, further preferably be less than 250nm's, further preferably be less than 100nm's, further preferably be less than the largest extension of 50nm, thereby make at least one the protection equipment with at least one stabilization additives preferably can not seal or stop up the pore of separator.Thus, protection equipment is restricted for the maximum capacity of stabilization additives.
In another embodiment; at least one the protection equipment with at least one stabilization additives is disposed at least one part at least in part, preferably at least one of electrochemistry single cell seal and/or at least one negative electrode at electrochemistry single cell on.The advantage that had is like this, the size of at least one protection equipment the and therefore maximum capacity of stabilization additives freely being selected substantially.
In another embodiment; at least one the first protection equipment with at least one stabilization additives is disposed in electrolyte at least in part and/or at least one the second protection equipment with at least one stabilization additives is disposed at least one part at least in part, preferably at least one is sealed and/or at least one negative electrode.Described at least one first protection equipment can separate with at least one the second protection battery limits, or has at least one stabilization additives different from stabilization additives in the second protection equipment.At least the first and at least the second protection equipment can be also identical or the stabilization additives that is arranged in protection equipment can be identical.
In one embodiment; at least one the protection equipment with at least one stabilization additives is formed by netted at least partly; wherein in this network structure, form at least in part (preferably forming by cavity) some regions, these regions can have at least one stabilization additives.Zeolite or similarly matrix structure are particularly preferably used as protection equipment in this case, also have further carbon nano-tube.
In one embodiment; there is the interaction (for example static or interaction covalently or non-covalently) of at least one protection equipment of at least one stabilization additives by chemistry and/or physics and be connected at least in part with SEI layer, particularly connect into make at least one protection equipment substantially can not by non-destructive separate with SEI layer surface.
The advantage that had is like this, can improve the mechanical stability of SEI layer thus, by at least one protection equipment is arranged on the electrolytical surface of being exposed to of SEI layer at least in part, the stereomutation of SEI layer is reduced, preferably reduce to minimum degree, preferably can be prevented from, and further can be at least in part when stereomutation will by least one stabilization additives near formed crackle or pore spatially, seal at least in part at the inner crackle occurring of SEI layer or pore, before the electrochemical active material surface reaction that can also expose when forming in crack at electrolyte in addition, react with it.
By the functionalization that is exposed to electrolytical surface of SEI layer, this surface is formed with at least part of chemistry and/or the Physical interaction with at least one protection equipment of at least one stabilization additives.
" functionalization " is current to be understood to, chemistry and/or physical measure are implemented in surface about SEI layer, its target is, forms at least in part atom, molecule, group, ion or its mixture that can be used in chemistry and/or Physical interaction on the surface of SEI layer.This can be for example by occurring by ionising radiation, heating, ozone, deposition process, acid or alkali, oxidation or reduction process or its mixed process.Make at least in part the material of protection equipment; it should be selected corresponding to applied functionalization; to obtain corresponding chemistry and/or Physical interaction between surperficial and at least one protection equipment of SEI layer; otherwise or, corresponding to the functional method of material of protection equipment, must be selected.
In one embodiment, this preferably realizes as follows: electrochemistry single cell is provided and on the electrochemical active material of negative electrode, produces stable SEI layer, for example, by the known method of prior art.Carry out for decomposing the step of electrochemistry single cell being positioned under the condition that obtains stable SEI layer on the electrochemical active material of negative electrode and then subsequently.Subsequently by not towards the formation of application function step practical function layer on the surface of the SEI layer of the electrochemical active material of negative electrode.Then at least one the protection equipment with at least one stabilization additives is applied to the surface being functionalized of SEI layer.
In one embodiment, at least one protection equipment designed to be used the hold-up vessel of at least one stabilization additives.Preferably; the protection equipment that is designed to hold-up vessel has and seals at least in part; this is sealed and can surround at least in part at least one stabilization additives; thereby make at least one stabilization additives only at it by least in part after at least one protection equipment discharges, can interact with SEI layer.In this case, by destroying at least in part protection equipment, cause the release of at least one stabilization additives.And on the other hand, at least part of energy of rupture of sealing for example, by using machining (stretch process (Zugarbeit)) and/or for example, for example, by chemical process (degradation reaction, ester cracking, disulphide cracking or ether-splitting solution) and/or for example, realize by physical process (melting is sealed).
In one embodiment; at least one protection equipment contacts with at least one battery monitoring device (preferably battery management system (BMS)) (preferably thermo-contact and/or electrically contact), and wherein this battery monitoring device can detect the irreversible capacitance loss of electrochemistry single cell.Preferably, the contacting of at least one protection equipment and at least one battery monitoring device (preferably thermo-contact and/or electrically contact) for example, realized by transmission equipment (wire or wire braid).When electrochemistry single cell according to the present invention experiences irreversible capacity loss during operation; the irreversible capacity loss of electrochemistry single cell is identified by BMS; it can contact with another one battery monitor system; and preferably by the transmission equipment that is preferably designed to wire or wire braid, at least one, protect equipment transmitted signal, this signal is thermal signal and/or the signal of telecommunication preferably.As to the preferably reaction of the described signal of thermal signal and/or the signal of telecommunication, at least one protection equipment discharges at least one stabilization additives at least in part.This preferably occurs by heating at least one protection equipment, and this protection equipment is partly destroyed thus, is preferably melted at least in part.
electrolyte
In one embodiment, electrochemistry single cell has at least one electrolyte.
Nonaqueous electrolyte (its by least one organic solvent and at least one alkali metal containing ion, preferably the inorganic or organic salt containing lithium ion forms) is applied as electrolyte.
In principle, all solvents in known to the skilled, the electrolyte that can add electrochemistry single cell can be as organic solvent.
Preferably, organic solvent is selected from following group: ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB), ethyl acetate (EA), 1, 2-dimethoxy-ethane, gamma-butyrolacton, oxolane (THF), 2-methyltetrahydrofuran, 1, 3-dioxolanes, sulfolane, ethyl-methyl sulfone (EMS), tetramethylene sulfone (TMS), fourth sulfone (BS), ethyl vinyl sulfone (EVS), the fluoro-2-of 1-(methyl sulphonyl) benzene (FS), acetonitrile or phosphate, or the mixture of these solvents.
Preferably, the salt of alkali metal containing ion, preferably the salt containing lithium ion has one or more counter ions (Gegenionen), and these counter ions are selected from following group: AsF 6 -, PF 6 -, PF 3(C 2f 5) 3 -, PF 3(CF 3) 3 -, BF 4 -, BF 2(CF 3) 2 -, BF 3(CF 3) -, [B (COOCOO) 2] -, [B (C 6h 5) 4] -, Cl -, Br -, AlCl 4 -, CF 3sO 3 -, C 4f 9sO 3 -, [(CF 3sO 2) 3c] -, [(CF 3sO 2) 2n] -, [(C 2f 5sO 2) N] -, [(CN) 2n] -, ClO 4 -, SiF 6 -or its mixture.
Preferably, the separator of electrochemistry single cell is by the wet stain of electrolyte.In one embodiment, separator is designed to the wet stain of electrolyte of ionic liquid.
Ionic liquid is ionic compound, its when room temperature in liquid state.Ionic liquid is by anion and cation composition, wherein the ratio between cation and anion be selected as its when room temperature not with lattice arrangement, can obtain liquid salt at ambient temperature thus, this salt is represented as ionic liquid.In this case, ionic liquid has conventionally " large " organic cation, and ethyl-methyl glyoxaline cation for example, for example, with relative " little " anion, tetrafluoro boric acid salt anionic.The attribute of ionic liquid also can be by the suitable combined effect of cation and anion.If alkali anion cyanate radical OCN for example -be used, ionic liquid also has more alkaline character like this.
Preferably, the ionic liquid that has a cation imdazole derivatives (particularly ethyl-methyl glyoxaline cation) is used.Preferably, anion can be selected from following group, AlCl 4, Al 2cl 7, F, F x HF, NO 2, NO 3, BF 4, AlF 4, PF 6, AsF 6, SbF 6, NbF 6, TaF 6, WF 7, CH 3cO 2, CF 3cO 2, C 3f 7cO 2, CH 3sO 3, CF 3sO 3, C 4f 9sO 3, (CF 3cO) (CF 3sO 3) N, (CF 3sO 2) 2n, (CF 3sO 2) (C 2f 5sO 2) N, (C 2f 5sO 2) 2n, (CF 3sO 2) 3c, (CN) 2n, (CN) 3c, CF 3bF 3, C 2f 5bF 3, C 3f 7bF 3, C 4f 9bF 3or its mixture.
In addition electrolysis mass-energy has and is arranged in electrolyte for the auxiliary material of the general application of lithium ion battery.For example this is free radical scavenger (for example biphenyl), flame-retardant additive (for example organophosphorus ester or hempa) or plumper (for example amine).
In addition electrolyte preferably has additive especially phenylene carbonic ester, fluorine-containing or not fluorine-containing organic boronic lithium, for example difluoro (oxalate closes) lithium borate (LiDFOB) or two (oxalate closes) lithium borate (LiBOB) and fluorine-containing or not fluorine-containing organic phosphoric acid lithium, for example tetrafluoro (oxalate closes) lithium phosphate (LiTFOP) or three (oxalate closes) lithium phosphate (LiTOP), it can affect the formation of SEI layer on electrode.
" electrochemistry single cell " is construed as the equipment with any type of electric form stored energy.This term therefore definition particularly once or the electrochemistry single cell of secondary type, but also defines the form of other accumulators, for example capacitor.Preferably, electrochemistry single cell is understood to lithium ion battery group/monocell.
In a preferred embodiment, electrochemistry single cell has at least one positive electrode, at least one negative electrode and at least one separator, this separator is separated positive electrode and negative electrode, and these positive electrodes, negative electrode and separator by least one seal at least in part around.
electrode
Term " negative electrode " meaning is that this electrode for example,, when being connected to load (motor), is exported electronics.Therefore, negative electrode is anode according to this convention.
Preferably, negative electrode has at least one electrochemical active material, and it is applicable to embed and/or discharge redox composition, particularly lithium ion.
In one embodiment, the electrochemical active material of negative electrode is selected from following group: the material of non-crystalline graphite, Scaly graphite, carbon containing or its mixture.
Preferably, negative electrode also has at least one other additive except electrochemical active material, preferably for improving the additive of conducting power, the additive based on carbon (for example carbon black) for example, and/or redox active additive, it reduces the destruction to electrochemical active material when overcharging electrochemistry single cell, preferably this destruction is reduced to minimum degree, preferably stops this destruction.
Preferably, negative electrode has metallic substrates.Preferably, this metallic substrates is applied by electrochemical active material at least in part.
In one embodiment, negative electrode has adhesive, and it can be used in and improves bonding between electrochemical active material and metallic substrates.Preferably this adhesive has polymer, fluorinated polymer preferably, and Kynoar preferably, it is with trade name
Figure BDA0000423445070000141
or
Figure BDA0000423445070000142
sold.
Term " positive electrode " meaning is that this electrode for example,, when being connected to load (motor), absorbs electronics.Therefore, positive electrode is negative electrode according to this convention.
Preferably, the positive electrode of electrochemistry single cell at least has a kind of electrochemical active material, and it is applicable to embed and/or discharge redox composition, particularly lithium ion.
In one embodiment, the electrochemical active material of positive electrode is selected from following group: at least one oxide, and mixed oxide preferably, it has one or more elements of selecting from nickel, manganese, cobalt, aluminium, phosphorus, iron or titanium.
In one embodiment, to have chemical formula be LiMPO to positive electrode 4compound, wherein M is at least one transition-metal cation, preferably the transition-metal cation of the first row of the transition metal of the periodic table of elements.
In the group that described at least one transition-metal cation preferably forms from the composition by manganese, iron, nickel, cobalt or titanium or these elements, select.Described compound preferably has olivine structural, and preferably senior olivine (ü bergeordnetes Olivin), is wherein particularly preferably iron or cobalt, preferably LiFePO 4or LiCoPO 4.But described compound also can have the structure that is different from olivine structural.
In another embodiment, positive electrode has oxide, preferably transition metal oxide, or transition metal mixed oxide, and the transition metal mixed oxide of spinel-type preferably, preferably LiMn2O4 (is preferably LiMn 2o 4), cobalt acid lithium (is preferably LiCoO 2) or lithium nickelate (be preferably LiNiO 2) or the mixture that formed by oxide described in two or three.But described oxide can be also the oxide that is different from spinel-type.
Further preferably, except aforementioned transition metal oxide, positive electrode can have lithium transition-metal mixed oxide or only have lithium transition-metal mixed oxide, and it comprises manganese, cobalt and nickel, and preferably lithium cobalt and manganese oxide (is preferably LiCoMnO 4), preferably Li, Ni, Mn oxide (is preferably LiNi 0.5mn 1,5o 4), preferably lithium-nickel-manganese-cobalt oxide (is preferably LiNi 0,33mn 0,33co 0,33o 2) or lithium nickel cobalt oxides (be preferably LiNiCoO 2), it can not exist with spinel-type or exist with spinel-type.
Preferably, except electrochemical active material, positive electrode also has at least one other additive, preferably for improving the additive of conducting power, the for example additive based on carbon (for example carbon black), and/or redox active additive, it reduces the destruction to electrochemical active material when overcharging electrochemistry single cell, preferably this destruction is reduced to minimum degree, preferably stop this destruction.
Preferably, positive electrode has adhesive, and it can be used in and improves bonding between electrochemical active material and metallic substrates.Preferably, this adhesive has polymer, fluorinated polymer preferably, and Kynoar preferably, it is with trade name
Figure BDA0000423445070000151
or
Figure BDA0000423445070000152
sold.
Preferably, positive electrode has metallic substrates.Preferably, this metallic substrates is applied by electrochemical active material at least in part.
Term " metallic substrates " preferably relates to the electrochemistry single cell assembly that is called as " electrode holder " and " current-collector ".Described metallic substrates is current to be suitable for Applied Electrochemistry active material and to be metalline substantially, preferably metalline completely.
Preferably, at least one electrode has metallic substrates at least in part.Preferably, this metallic substrates is designed to paper tinsel or web frame or netted braid at least in part, preferably has metal.
In one embodiment, metallic substrates has the alloy of copper or cupric.In another embodiment, metallic substrates has aluminium.In one embodiment, metallic substrates can be designed to paper tinsel, web frame or netted braid, and it is preferably has plastics at least in part.
Preferably, in the whole surface of metallic substrates, reach 30%, preferably reach 50%, preferably reach 70%, preferably reach 100% part and there is at least one layer, this layer at least has a kind of electrochemical active material, and it is applicable to embed and/or discharge lithium ion.
separator
In one embodiment, separator is used, and its positive electrode and negative electrode are separated, and is non-electron conduction or only very poor electron conduction, and it is by allowing at least in part the carrier of material permeance to form.Described carrier preferably applies by inorganic material at least one side.Preferably use inorganic material as the carrier that allows at least in part material permeance, it is preferably configured to the Wei Lansi (Vlies) of nonwoven.
(it preferably has polymer to described inorganic material, and be particularly preferably one or more polymer of selecting from polyethylene terephthalate (PET), polyolefin or polyethers), it applies with material inorganic, that be preferably ionic conduction, this material is also preferably the temperature range intermediate ion conduction of-40 ℃ to 200 ℃, and preferably have from least one compound at least one the group of oxide, phosphate, silicate, titanate, sulfate, aluminosilicate in element Zr, Al, Li, be particularly preferably and comprise zirconium dioxide.
Preferably, the material of the inorganic ionic conduction of separator has the particle that maximum gauge is less than 100nm, especially from 0.5 to 7 μ m, preferably from 1 to 5 μ m, the particle of from 1.5 to 3 μ m preferably.
In one embodiment, described separator have be positioned on Wei Lansi and among the inorganic coating of porous, its have mean particle size be 0.5 to 7 μ m, preferably from 1 to 5 μ m's and be particularly preferably the alumina particle of from 1.5 to 3 μ m, the oxide of these particles and element Zr or Si sticks together.
For obtaining much higher as far as possible cell size, in all particles preferred weight percent more than 50% particle and particularly preferably percentage by weight more than 80% particle the border in above-mentioned mean particle size.Preferably, maximum granular size be preferably used Wei Lansi thickness 1/3 to 1/5 and be particularly preferably be less than or equal to its 1/10.
Suitable polyolefin is preferably polyethylene, polypropylene or polymethylpentene.It is particularly preferably polypropylene.Equally, can consider to use polyamide, polyacrylonitrile, Merlon, polysulfones, polyether sulfone, Kynoar, polystyrene as inorganic carrier material.Can also use the mixture of polymer.
Have PET as the separator of carrier material with trade name
Figure BDA0000423445070000171
in market, can buy.Described separator can be manufactured according to disclosed method in EP 1 017 476.
Term " Wei Lansi of the nonwoven " meaning is, the polymer existing with the form of the fiber (non-woven fabric) of non-intertexture form.The known this Wei Lansi of prior art and/or can be manufactured according to known method, for example, for example, manufacture by spunbond process or melt blown process (introducing in DE 195 01 271 A1).
Preferably, separator has Wei Lansi, and the average thickness that this Wei Lansi has is 5 to 30 μ m, preferably from 10 to 20 μ m.Preferably, be designed to can be flexible for described Wei Lansi.Preferably, Wei Lansi has uniform pore radius and distributes, and preferably to have pore radius be 75 to 100 μ m at least 50% hole.Preferably, Wei Lansi has 50% vesicularity, preferably from 50 to 97% vesicularity.
The volume (100%) that " vesicularity " is defined as Wei Lansi deducts the volume (corresponding to the part of the volume not filled up by material in Wei Lansi) of tieing up blue silk fiber.In this case, the volume energy of Wei Lansi is calculated by the size of Wei Lansi.The volume of fiber is drawn by the measured weight of considered Wei Lansi and the thickness of polymer fiber.The large vesicularity of Wei Lansi also makes separator have more much higher cell size to become possibility, therefore can realize the absorption higher to electrolyte with separator.
In another embodiment, separator is by PETG, polyolefin, polyethers, polyamide, polyacrylonitrile, Merlon, polysulfones, polyether sulfone, Kynoar, polystyrene or its compositions of mixtures.Preferably, separator is formed by polyolefin or by polyolefinic mixture.Particularly preferably, in this embodiment separator by polyethylene and polyacrylic compositions of mixtures.
Preferably, this separator has the layer thickness of from 3 to 14 μ m.
Polymer is preferably tieed up blue filate formula with fiber and is existed, and the average diameter that wherein polymer fiber preferably has is 0.1 to 10 μ m, preferably from 1 to 4 μ m.
" mixing " of term polymer or " mixture " look like, and polymer is preferably tieed up blue filate formula with it and existed, and this Wei Lansi is connected mutually layer by layer.This Wei Lansi or Wei Lansi compound for example have disclosed in EP 1 852 926.
In another embodiment of separator, separator is comprised of inorganic material.Preferably, magnesium, calcium, aluminium, silicon and titanyl compound are used as inorganic material and use, and silicate and zeolite, borate and phosphate are also like this in addition.This material for separator and the method for manufacturing this separator have disclosed at EP 1,783 852.In the preferred embodiment of separator embodiment, separator is comprised of magnesium oxide.
In another embodiment of separator, the part that in magnesium oxide, percentage by weight is 50 to 80% can be replaced by the mixture of calcium oxide, barium monoxide, brium carbonate, lithium phosphate, sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, barium phosphate or lithium borate, Boratex, potassium borate or these compounds.
Preferably, the separator of this embodiment has the layer thickness of from 4 to 25 μ m.
According to the present invention; have equally a kind of for making the method for electrochemistry single cell work; wherein electrochemistry single cell has at least one stabilization additives; when SEI layer is unstable or become unstable; or particularly once be at or above or below predetermined parameter, described additive is discharged from least one protection equipment at least in part.
In addition, the invention still further relates to for the manufacture of according to the method for electrochemistry single cell of the present invention, it comprises the steps:
● at least one positive electrode is provided
● at least one negative electrode is provided, and wherein this at least one negative electrode has in fact the electrochemical active material of at least one carbon containing, and this active material can form SEI layer at least some parts on surface
● at least one stabilization additives is provided, and it can be used in stablizes SEI layer
● at least one protection equipment is provided, and it can be used in and absorbs at least in part described at least one stabilization additives
Wherein, when being at or above or below at least one predetermined parameter about SEI layer, described at least one stabilization additives is discharged from described at least one protection equipment.
According to electrochemistry single cell of the present invention, can be applied to as mobile information apparatus, instrument, electric automobile and power with the automobile of hybrid power driving.
Fig. 1 is schematically illustrated according to the structure of the embodiment of electrochemistry single cell of the present invention;
Fig. 2 be shown schematically in SEI layer become unstable before and on time point afterwards, there is structure and the layout of the negative electrode of SEI layer and the embodiment of protection equipment, wherein negative electrode and protection equipment are as according to the part of electrochemistry single cell of the present invention;
Fig. 3 be shown schematically in SEI layer become unstable before and protection equipment and there is structure and the layout of embodiment of the negative electrode of SEI layer on time point afterwards, wherein protect equipment and negative electrode as according to the part of electrochemistry single cell of the present invention.
Fig. 1 illustrates according to electrochemistry single cell 100 of the present invention; it is comprised of following part: have active material positive electrode 110, separator 120, seal 160, there is the negative electrode 150 of active material, the lip-deep SEI layer 170 that is positioned at the negative electrode 150 with active material and stabilization additives or stabilization additives mixture 180, this stabilization additives or additive agent mixture seal 190 of protection equipment being designed to the separator between SEI layer 170 and stabilization additives 180 between 160 some parts around.In addition, electrochemistry single cell 100 has battery management system 131, and it contacts with positive electrode 110 and negative electrode 150 and battery monitor system 132.By transmission equipment 140, battery monitor system 132 is connected with protection equipment 190.The some parts of transmission equipment 140 and protection equipment 190 have the relation of operability.This advantage providing is; measuring, to the irreversible capacitance loss of electrochemistry single cell 100, (this capacitance loss can evaluate according to the symbol of exterior visual; SEI layer 107 is unsettled or becomes unstable) time; by battery management system 131, this capacitance loss is conveyed to battery monitor system 132, this battery monitor system can be given protection equipment 190 signal transmissions by transmission equipment 140.Preferably, described signal relates to the signal of telecommunication, and this signal is transferred in transmission equipment 140.In this case; transmission equipment 140 at least forms resistance in transmission equipment 140 and protection equipment 190 have the region of relation of operability; its electric energy; in other words the described signal of telecommunication; energy transform into heat energy; the operability relation of this heat energy based between transmission equipment 140 and protection equipment 190 outputed on protection equipment 190 at least in part, and described stabilization additives or stabilization additives mixture 180 discharge from protection equipment 190 thus.In this case, protection equipment 190 is destroyed at least in part, for example, melted and destroy.Therefore described stabilization additives or stabilization additives mixture 180 can interact with SEI layer 170, and preferably make SEI layer 170 stable.Protection equipment 190 has at least one polymer; it has melting temperature; this melting temperature is higher than electrochemistry single cell 100 normal work period common temperature in this electrochemistry single cell 100, but is less than the temperature that the resistance region by transmission equipment 140 produces.
Fig. 2 illustrates according to the negative electrode of electrochemistry single cell of the present invention and (discharges the part of protecting equipment before stabilization additives 250: 231 from the some parts of protection equipment 231,232; Discharge the part of protecting equipment after stabilization additives 250: 232) discharge before stabilization additives or stabilization additives mixture 250 201 and afterwards 202.In this case, negative electrode 201,202 has electrochemical active material 210, and it is applied by SEI layer 220 at least in part.A side that deviates from electrochemical active material 210 in SEI layer 220 is functionalized (in Fig. 2, not describing), protects thus the some parts of equipment 231,232 substantially can not nondestructively from SEI layer 220, disassemble by connecting 240.These connect 240 can be that for example covalent bond, static connect or other strong interaction or connections.In addition, the some parts that comprises stabilization additives or stabilization additives mixture 250 in protection equipment 231,232 is connected to each other by connecting 260 equally, thereby makes the some parts of protection equipment 231,232 substantially can not be nondestructively separated from each other.In addition likely, the some parts of protection equipment 231,232 has weakness 271,272, preferably destroyed at the some parts of these weakness protection equipment 231,232.This is for example accompanied by the stereomutation of SEI layer 220 and progressively occurs preferably when SEI layer 220 becomes unstable.Subsequently, protection equipment 231, 232 some parts not only by the connection 240 that substantially can not nondestructively remove, be connected with SEI layer 220 and but also by 260 being interconnected with one another being connected of substantially can not nondestructively removing, substantially intact part (this part comprises stabilization additives or stabilization additives mixture 250) damaged 232 before in protection equipment 231, stabilization additives or stabilization additives mixture 250 are released, and can make SEI layer 220 stablize and preferably also can repair SEI layer 220, this realizes by embedding the method for the some parts of SEI layer 220.In protection equipment 232, the damage of some parts preferably occurs in these weakness 270.
Fig. 3 illustrates according to the negative electrode of electrochemistry single cell of the present invention before discharging stabilization additives or stabilization additives mixture 340 from protection equipment 331,332 301 and afterwards 302.In this case, negative electrode 301,302 is comprised of the electrochemical active material 310 being applied by SEI layer 320 at least in part.Protection equipment 331,332 is preferably located in electrolyte solution 350., when SEI layer 320 becomes unstable, can, at inner cracking or the pore of forming of SEI layer 320, make thus electrochemical active material 310 to be exposed at least in part electrolyte solution 350 now.When SEI layer 320 becomes unstable, stabilization additives or stabilization additives mixture 340 are discharged 332 from protection equipment, and embed SEI layer 320 now, make thus this SEI layer again stable.

Claims (9)

1. an electrochemistry single cell, described electrochemistry single cell has at least one negative electrode, at least one positive electrode and at least one electrolyte, wherein said at least one negative electrode has in fact the electrochemical active material of at least one carbon containing, described electrochemical active material can form " solid electrolyte interface " layer at least some surperficial parts of described electrode, it is SEI layer
It is characterized in that,
Described electrochemistry single cell has at least one stabilization additives; described additive can be used in and makes described SEI layer stable; at least one protection equipment is wherein set in described electrochemistry single cell; described at least one protection equipment has described at least one stabilization additives and is preferably designed to be hold-up vessel; while being wherein at or above or below at least one predetermined parameter about described SEI layer, described at least one stabilization additives is discharged from described at least one protection equipment at least in part.
2. electrochemistry single cell as claimed in claim 1; it is characterized in that; described at least one protection equipment has the first shape and the second shape; wherein as the content that is at or above or below at least one predetermined parameter, particularly temperature, pressure, pH value, chemical compound about described SEI layer particularly HF, H 2o, CO 2content, the capacitance loss of monocell or during the combination of voltage or these parameters, described at least one protection equipment is from described the first change of shape to described the second shape, wherein said protection equipment discharges described stabilization additives with the second shape.
3. as electrochemistry single cell in any one of the preceding claims wherein, it is characterized in that, described at least one protection equipment has at least one macromolecular material.
4. as electrochemistry single cell in any one of the preceding claims wherein, it is characterized in that, described at least one stabilization additives is from phenylene carbonic ester, sub-vinyl carbonate, fluorine-containing or not fluorine-containing organic boronic lithium, difluoro (oxalate closes) lithium borate (LiDFOB) or two (oxalate closes) lithium borate (LiBOB) and fluorine-containing or not fluorine-containing organic phosphoric acid lithium, tetrafluoro (oxalate closes) lithium phosphate (LiTFOP), three (oxalate closes) lithium phosphate (LiTOP), or compound dynamics and/or thermodynamically stable electric insulation and/or ionic conduction, dynamics and/or thermodynamically stable lithium salts, inorganic lithium salt, LiF, LiOH, Li 2cO 3and Li 2in O or its mixture, select.
5. as electrochemistry single cell in any one of the preceding claims wherein, it is characterized in that, described negative electrode has the electrochemical active material of at least one carbon containing, and described electrochemical active material is selected from non-crystalline graphite, Scaly graphite, carbonaceous material or its mixture.
6. as electrochemistry single cell in any one of the preceding claims wherein, it is characterized in that, described positive electrode has at least one electrochemical active material at least in part, and described at least one electrochemical active material is selected from following group:
● at least one compound L iMPO 4, wherein M is the transition-metal cation that at least one selects from the combination of manganese, iron, cobalt, titanium or these elements; Or
● the lithium metal oxide of at least one spinel-type or lithium metal mixing oxide, wherein said metal is selected from cobalt, manganese or nickel; Or
● the lithium metal oxide of at least one non-spinel-type or lithium metal mixing oxide, wherein said metal is selected from cobalt, manganese or nickel; Or
Its mixture.
7. one kind for making the method for electrochemistry single cell work in any one of the preceding claims wherein; it is characterized in that; when described SEI layer is unstable or become unstable; particularly, once be at or above or below predetermined parameter, described at least one stabilization additives is discharged from described at least one protection equipment at least in part.
8. for making a method for the electrochemistry single cell work described in claim 1 to 6 any one, described method comprises the steps:
● at least one positive electrode is provided
● at least one negative electrode is provided, and wherein said at least one negative electrode has in fact the electrochemical active material of at least one carbon containing, and described electrochemical active material can form described SEI layer at least some parts on surface
● at least one stabilization additives is provided, and described at least one stabilization additives can make described SEI layer stable
● at least one protection equipment is provided, and described at least one protection equipment can be used in and absorbs at least in part described at least one stabilization additives
It is characterized in that, when being at or above or below at least one predetermined parameter about described SEI layer, described at least one stabilization additives is discharged from described at least one protection equipment.
9. the purposes that in claim 1 to 6, the electrochemistry single cell described in any one is used to load to power, the particularly purposes in mobile information apparatus, instrument, electric automobile or the automobile that drives with hybrid power.
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