CN106784778B - Electrode material and preparation method thereof with sensitive characteristic - Google Patents
Electrode material and preparation method thereof with sensitive characteristic Download PDFInfo
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- CN106784778B CN106784778B CN201611091355.1A CN201611091355A CN106784778B CN 106784778 B CN106784778 B CN 106784778B CN 201611091355 A CN201611091355 A CN 201611091355A CN 106784778 B CN106784778 B CN 106784778B
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M10/05—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
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
- H01M2200/106—PTC
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- 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
Abstract
The invention belongs to technical field of lithium ion, more particularly to a kind of electrode material and preparation method thereof with sensitive characteristic, the electrode material includes the core formed by lithium metal oxide, and the shell formed by polythiofuran derivative, the weight proportion of the total electrode material of polythiofuran derivative Zhan is 0.1%~8%, and the Curie temperature of the polythiofuran derivative is 90 ~ 130 DEG C.Compared with the prior art, the present invention has excellent sensitive characteristic by the electrode material that polythiofuran derivative coats the core-shell structure that lithium metal oxide is formed, i.e. each active particle all has positive temperature-sensitivity coefficient feature；When the internal temperature of battery rising using the electrode material reaches the Curie temperature of the material, the resistance value of electrode material sharply increases, so that the conductive network between each electrode material granules is blocked, electron transfer speed substantially reduces, it effectively prevent battery to further heat up, to improve the safety of battery.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of electrode materials and its system with sensitive characteristic
Preparation Method.
Background technique
Although lithium ion battery has been widely used in daily life, its safety issue is always by pass
Note, this is also its large-scale application one bottleneck urgently to be resolved when power battery.Because lithium ion battery is by having height
The electrode of reactivity and incendive organic electrolyte composition, it is very big that this results in lithium ion battery to have in security performance
Birth defects.Lithium ion battery is under abuse conditions, it is possible to create a large amount of heat is so that internal temperature of battery is anxious
Play, which rises, to be led to thermal runaway and then leads to the serious accidents such as on fire or explosion.
In general, the thermal stability of battery is a key factor of its safety, and battery generates thermal runaway
Root is certain reactions at electrode and electrolyte liquor interface again.The heat that these reactions generate, so that internal temperature of battery rises, this is again
The progress of exothermic reaction is promoted in turn, so that the temperature of inside battery is further up, and may be caused in turn more
Exothermic reaction so as to form a kind of vicious circle of chain type, and eventually leads to temperature and steeply rises and thermal runaway.Therefore,
How to avoid battery that thermal runaway occurs is the key that solve the problems, such as cell safety.
For this purpose, industry researcher has also made some relevant explorations and research.For example, the PTC that temperature coefficient is positive is (just
Temperature coefficient) with positive temperature-responsive feature, it can increased dramatically material in its resistance of near Curie temperature；Based on this, existing rank
The some commercial battery groups of section are generally in external incidentally upper PTC element or in the subsidiary upper PTC element of battery cephalosome, but these yuan
Part cannot play timely monitoring and inhibiting effect far from electrode and electrolyte liquor interface, to thermal runaway.In addition, such as patent
In ZL200410080958.2 and CN 104409681A, plus plate current-collecting body and anode material between or negative current collector and
One layer of ptc layer is arranged between the material of cathode can improve to a certain extent in this way to be made into PTC combination electrode
The security performance of battery, but due to there is no the protection of ptc material on positive electrode and negative electrode material, this kind of PTC compound electric
Pole is only capable of the electric current between cutting collector and electrode material coating or between electrode active material particles and transmits, and can not close
The risk exothermic auxiliary reaction that high activity electrode material surface is occurred directly under high temperature, still there is the danger of thermal runaway.Also just like
In patent CN1606183A, when preparing electrode, that is, during being homogenized, by ptc material and cathode metal oxide, conduction
Agent, binder mix, and will cause ptc material being unevenly distributed on pole piece in this way, so as to cause battery resistance value compared with
Greatly or when safety problem occurs for battery, hot-spot cannot ensure the safety of battery to cause thermal runaway on pole piece.
In addition, the Curie temperature of ptc material at this stage is relatively high, generally between 130~150 DEG C, this and battery
Used in temperature (135 DEG C or so) range of polypropylene, polyethylene composite diaphragm role have some overlappings, and for
For many systems, the exothermic reaction in electrode/electrolyte interface at 130 DEG C than more significant, when reaching 150 DEG C or so
Thermal runaway has been difficult to avoid, therefore existing PTC technology can have lag even in the safeguard protection of lithium ion battery
Protect infull deficiency.
In view of this, how to make each active particle in electrode that all there is positive temperature-sensitivity coefficient (PTC) feature, and
And promptly can be changed into insulation state from conventional conductive state in the case where needing the sensitive temperature controlled, then, occur at this time
All electrochemical reactions on active particle surface will be shut off promptly, and battery is avoided to enter dangerous thermal runaway state.
Summary of the invention
It is an object of the invention to: in view of the deficiencies of the prior art, and a kind of electrode material with sensitive characteristic is provided,
The battery material has sensitive response characteristic to heated, high current, can effectively promote the security performance of lithium ion battery.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of electrode material with sensitive characteristic, spreads out including the core formed by lithium metal oxide, and by polythiophene
The shell that biology is formed, the weight proportion of the total electrode material of polythiofuran derivative Zhan are 0.1%~8%, and the polythiophene spreads out
The Curie temperature of biology is 90~130 DEG C.
The present invention selects the reason of polythiofuran derivative is as covering material, on the one hand, polythiofuran derivative is conductive poly-
Close object, itself have excellent environmental stability and it is good lead Electronic Performance, be fully able to play the role of conductive agent, because
This, when being used for the electrode material to make electrode slice, can add less or conductive agent is not added, to save production cost；Another party
Face, the Curie temperature of polythiofuran derivative are 90~130 DEG C, within this temperature range, the resistance of polythiofuran derivative sharply on
It rises, so that the conductive network between each electrode material granules is blocked, electron transfer speed is substantially reduced, and effectively prevent battery into one
Step heating, to improve the safety of battery.
Therefore, when battery is by misuse or overcharge, due to the resistance energy of the polythiofuran derivative with positive temperature coefficient
Rise with temperature and sharply increases, thus interruptive current, therefore can be avoided hot mistake using the lithium ion battery of the electrode material
On fire or explosion danger caused by control.Generally, the resistance of polythiofuran derivative can increase suddenly when being higher than its Curie temperature
Add.If the Curie temperature of polythiofuran derivative is selected to be lower than 90 DEG C, its inside when lithium ion battery carries out charge or discharge
Temperature is possible to that 90 DEG C can be risen towards, if the resistance value of polythiofuran derivative increases lower than 90 DEG C, will affect battery
Normal charge and discharge.In addition, the resistance of battery is being higher than 130 if the Curie temperature of selection polythiofuran derivative is higher than 130 DEG C
DEG C just increase, and this temperature has been approached the closed pore temperature of battery isolating film, in this way before resistance increases, lithium ion battery is past
Toward will cause thermal runaway, it cannot ensure the safety of battery.Therefore, the Curie temperature value of polythiofuran derivative of the present invention is big
Small is extremely crucial.
In addition, if the weight proportion of the total electrode material of polythiofuran derivative Zhan less than 0.1%, due to ptc characteristics
The amount of polythiofuran derivative is very little, can exist and coat non-uniform situation, cannot guarantee the safety of battery well；If polythiophene
The weight proportion of the total electrode material of derivative Zhan is greater than 8%, then due to the shell of the polythiofuran derivative formation with ptc characteristics
It is too thick, it is unfavorable for the circulation of lithium ion, the reduction such as cycle performance and capacity characteristic of lithium ion battery can be made.Therefore, of the invention
The size of the weight proportion of polythiofuran derivative is also vital.
Wherein, the present invention has the specific mechanism of action of the electrode material of sensitive characteristic are as follows: in charging, polythiophene is derivative
Object carries out electrochemical oxidation doping, and polythiofuran derivative conductivity improves after doping, so polythiofuran derivative coats under room temperature
The electrode material conductivity of lithium metal oxide is high, will not influence electrode reaction；When temperature is higher than the Curie of polythiofuran derivative
When temperature, the alkyl chain movement velocity in polythiofuran derivative molecule is accelerated, and the conjugated degree of molecule is caused to be deteriorated, simultaneously because
Hot removing impurities occurs for the polythiofuran derivative of doping and dopant thermally decomposes, and leads to the resistance of polythiofuran derivative clad
It increases sharply, to prevent continuing for discharge and recharge reaction, avoids battery that thermal runaway occurs.
There is a kind of improvement of the electrode material of sensitive characteristic, the total electrode material of polythiofuran derivative Zhan as the present invention
The weight proportion of material is 1%~5%, this is the preferred specific gravity of polythiofuran derivative of the present invention.
There is a kind of improvement of the electrode material of sensitive characteristic, the total electrode material of polythiofuran derivative Zhan as the present invention
The weight proportion of material is 3%, this is the preferable specific gravity of polythiofuran derivative of the present invention.
There is a kind of improvement of the electrode material of sensitive characteristic, the Curie temperature of the polythiofuran derivative as the present invention
It is 100~120 DEG C, this is the preferred Curie temperature value range of polythiofuran derivative of the present invention.
There is a kind of improvement of the electrode material of sensitive characteristic, the Curie temperature of the polythiofuran derivative as the present invention
It is 110 DEG C, this is the preferable Curie temperature value of polythiofuran derivative of the present invention.
There is a kind of improvement of the electrode material of sensitive characteristic as the present invention, the polythiofuran derivative is poly- 3- hexyl
Thiophene, poly- 3- octyl thiophene, poly- 3- nonyl thiophene, poly- 3- decylthiophene, poly- 3- undecyl thiophene, gathers poly- 3- heptyl thiophene
At least one of 3- dodecylthiophene, poly- 3- tridecyl thiophene and poly- 3- myristyl thiophene.Selected polythiophene spreads out
Within the scope of 90~130 DEG C, and with the growth of alkyl chain, the Curie temperature of polythiofuran derivative becomes the Curie temperature of biology
It is low；And these polythiofuran derivatives all have stronger thermal sensitive effect, and it can be timely and effectively when being more than its Curie temperature
Interruptive current avoids catching fire and exploding etc. dangerous.
There is a kind of improvement of the electrode material of sensitive characteristic as the present invention, the lithium metal oxide is LiCoO2、
LiNiO2、LiMn2O4、LiaNibCocMndO2、LiaNibCocAldO2And LiFePO4At least one of, wherein 0.95≤a≤
1.05,0 < b <, 1,0 < c <, 1,0 < d < 1.
Another object of the present invention is to provide a kind of preparation method of above-mentioned electrode material with sensitive characteristic,
The following steps are included:
Step 1: lithium metal oxide and polythiofuran derivative powder are weighed according to weight ratio, by polythiofuran derivative
Powder is dissolved in organic solvent, is then slowly added into lithium metal oxide, is sufficiently stirred, and uniform dispersion is obtained；
Step 2: dispersion liquid is dried 2~6h at 100~160 DEG C, polythiofuran derivative is made to be evenly coated at lithium
Metal oxide surface to get arrive the electrode material.
There is a kind of improvement of the preparation method of the electrode material of sensitive characteristic as the present invention, the organic solvent is chlorine
Imitative, tetrahydrofuran, N-Methyl pyrrolidone or combinations thereof.The polythiofuran derivative has good dissolution in these solvents
Property, but the polythiofuran derivative does not dissolve in electrolyte, therefore electrolyte will not occur by lithium metal oxide material surface
The case where polythiofuran derivative clad dissolves.
There is a kind of improvement of the preparation method of the electrode material of sensitive characteristic, the speed stirred in step 1 as the present invention
Degree is 1500~3000r/min.Mixing speed is too low, and dispersion is uneven；Mixing speed is excessively high, and it is derivative may to destroy polythiophene
The molecular structure of object.
Compared with the prior art, the present invention at least has the advantages that
1) present invention has by the electrode material that polythiofuran derivative coats the core-shell structure that lithium metal oxide is formed
Excellent sensitive characteristic, i.e. each active particle all have positive temperature-sensitivity coefficient (PTC) feature；When on internal temperature of battery
When liter reaches the Curie temperature of the electrode material, the resistance value of electrode material is sharply increased, and electric current and heat will be obtained significantly
Control, then the micropore closed effect for cooperating isolation film itself, the temperature of battery would become hard to rise, even if temperature rises to isolation film
Broken film temperature, positive and negative pole material generates the contact of area, and due to its storeroom electric conductivity it is difficult be also difficult to generate compared with
Big heat, so the security performance of the battery made through the invention will be greatly improved.
2) present invention have sensitive characteristic electrode material preparation method simple process, it is easy to operate, production cost compared with
It is low, it is suitable for enterprise scale and produces.
Specific embodiment
The present invention and its advantages are described in further detail below in conjunction with specific embodiment, but tool of the invention
Body embodiment is without being limited thereto.
Embodiment 1
LiNi is weighed according to the weight ratio of 92:81/3Co1/3Mn1/3O2With poly- 3- hexyl thiophene powder, by poly- 3- hexyl thiophene
Pheno powder is dissolved in chloroform, is then slowly added into LiNi1/3Co1/3Mn1/3O2, it is sufficiently stirred under the revolving speed of 2000r/min,
Obtain uniform dispersion；Dispersion liquid is dried 4h at 130 DEG C, poly- 3- hexyl thiophene is made to be evenly coated at LiNi1/3Co1/ 3Mn1/3O2Surface to get arrive the positive electrode with sensitive characteristic；The positive electrode obtained by the preparation method
Curie temperature is 130 DEG C.
Embodiment 2
LiNi is weighed according to the weight ratio of 95:51/3Co1/3Al1/3O2With poly- 3- heptyl thiophene powder, by poly- 3- heptyl thiophene
Pheno powder is dissolved in tetrahydrofuran, is then slowly added into LiNi1/3Co1/3Al1/3O2, sufficiently stirred under the revolving speed of 2500r/min
It mixes, obtains uniform dispersion；Dispersion liquid is dried 3h at 150 DEG C, poly- 3- heptyl thiophene is made to be evenly coated at LiNi1/ 3Co1/3Al1/3O2Surface to get arrive the positive electrode with sensitive characteristic；The positive material obtained by the preparation method
The Curie temperature of material is 125 DEG C.
Embodiment 3
LiCoO is weighed according to the weight ratio of 99:12With poly- 3- octyl thiophene powder, poly- 3- octyl thiophene powder is dissolved
In N-Methyl pyrrolidone, it is then slowly added into LiCoO2, it is sufficiently stirred under the revolving speed of 3000r/min, is uniformly divided
Dispersion liquid；Dispersion liquid is dried 2h at 160 DEG C, poly- 3- octyl thiophene is made to be evenly coated at LiCoO2Surface to get arrive institute
The positive electrode with sensitive characteristic stated；The Curie temperature of the positive electrode obtained by the preparation method is 120 DEG C.
Embodiment 4
LiNiO is weighed according to the weight ratio of 94:62With poly- 3- nonyl thiophene powder, poly- 3- nonyl thiophene powder is dissolved
In chloroform, it is then slowly added into LiNiO2, it is sufficiently stirred under the revolving speed of 1500r/min, obtains uniform dispersion；It will dispersion
Liquid is dried 5h at 140 DEG C, and poly- 3- nonyl thiophene is made to be evenly coated at LiNiO2Surface has temperature-sensitive to get to described
The positive electrode of characteristic；The Curie temperature of the positive electrode obtained by the preparation method is 115 DEG C.
Embodiment 5
LiMn is weighed according to the weight ratio of 96:42O4With poly- 3- decylthiophene powder, poly- 3- decylthiophene powder is dissolved
In N-Methyl pyrrolidone, it is then slowly added into LiMn2O4, it is sufficiently stirred under the revolving speed of 2800r/min, is uniformly divided
Dispersion liquid；Dispersion liquid is dried 6h at 100 DEG C, poly- 3- decylthiophene is made to be evenly coated at LiMn2O4Surface to get arrive institute
The positive electrode with sensitive characteristic stated；The Curie temperature of the positive electrode obtained by the preparation method is 110 DEG C.
Embodiment 6
LiFePO is weighed according to the weight ratio of 97:34With poly- 3- undecyl thiophene powder, by poly- 3- undecyl thiophene
Pheno powder is dissolved in tetrahydrofuran, is then slowly added into LiFePO4, it is sufficiently stirred, is obtained under the revolving speed of 1800r/min
Even dispersion liquid；Dispersion liquid is dried 4.5h at 110 DEG C, poly- 3- undecyl thiophene is made to be evenly coated at LiFePO4Table
Face to get arrive the positive electrode with sensitive characteristic；Pass through the Curie temperature for the positive electrode that the preparation method obtains
It is 105 DEG C.
Embodiment 7
Li is weighed according to the weight ratio of 99.9:0.11.05Ni1/3Co1/3Mn2/3O2It, will with poly- 3- dodecylthiophene powder
Poly- 3- dodecylthiophene powder is dissolved in tetrahydrofuran, is then slowly added into Li1.05Ni1/3Co1/3Mn2/3O2, in 1800r/
It is sufficiently stirred under the revolving speed of min, obtains uniform dispersion；Dispersion liquid is dried 2.5h at 120 DEG C, makes poly- 3- dodecane
Base thiophene is evenly coated at Li1.05Ni1/3Co1/3Mn2/3O2Surface to get arrive the positive electrode with sensitive characteristic；It is logical
The Curie temperature for crossing the positive electrode of preparation method acquisition is 100 DEG C.
Embodiment 8
Li is weighed according to the weight ratio of 99.5:0.51.05Ni1/3Co1/3Al2/3O2It, will with poly- 3- tridecyl thiophene powder
Poly- 3- tridecyl thiophene powder is dissolved in chloroform, is then slowly added into Li1.05Ni1/3Co1/3Al2/3O2, 2200r/min's
It is sufficiently stirred under revolving speed, obtains uniform dispersion；Dispersion liquid is dried 3.5h at 125 DEG C, makes poly- 3- tridecyl thiophene
Pheno is evenly coated at Li1.05Ni1/3Co1/3Al2/3O2Surface to get arrive the positive electrode with sensitive characteristic；By this
The Curie temperature for the positive electrode that preparation method obtains is 95 DEG C.
Embodiment 9
LiFePO is weighed according to the weight ratio of 98:24With poly- 3- myristyl thiophene powder, by poly- 3- myristyl thiophene
Pheno powder is dissolved in chloroform, is then slowly added into LiFePO4, it is sufficiently stirred under the revolving speed of 2600r/min, is uniformly divided
Dispersion liquid；Dispersion liquid is dried 5.5h at 135 DEG C, poly- 3- myristyl thiophene is made to be evenly coated at LiFePO4Surface, i.e.,
Obtain the positive electrode with sensitive characteristic；The Curie temperature of the positive electrode obtained by the preparation method is 90
℃。
Embodiment 10
LiCoO is weighed according to the weight ratio of 97:1.5:1.52, poly- 3- octyl thiophene and poly- 3- dodecylthiophene powder
Poly- 3- octyl thiophene and poly- 3- dodecylthiophene powder are dissolved in chloroform, are then slowly added into LiCoO by end2, In
It is sufficiently stirred under the revolving speed of 2500r/min, obtains uniform dispersion；Dispersion liquid is dried 4.5h at 125 DEG C, makes poly- 3-
Octyl thiophene and poly- 3- dodecylthiophene are evenly coated at LiCoO2Surface to get arrive the anode with sensitive characteristic
Material；The Curie temperature of the positive electrode obtained by the preparation method is 110 DEG C.
The positive electrode obtained in Examples 1 to 10 with sensitive characteristic is fabricated to positive plate respectively, then with it is negative
Pole piece and isolation film are assembled into battery core by the mode of winding, later by encapsulation, fluid injection (lithium salt 1mol/L), quiet
It sets, be melted into, fixture baking, being evacuated the processes such as molding and partial volume, lithium ion battery is prepared.Wherein, using Examples 1 to 10
Positive electrode made of battery number consecutively be S1-S10.
The positive electrode of processing uncoated in Examples 1 to 5 is fabricated to positive plate, then with negative electrode tab and isolation film
It is assembled into battery core by the mode of winding, is dried later by encapsulation, fluid injection (lithium salt 1mol/L), standing, chemical conversion, fixture
The processes such as roasting, pumping molding and partial volume, are prepared lithium ion battery, the number of battery is followed successively by D1-D5.
It is respectively S1-S10 to number and the battery of D1-D5 progress overcharge test, firstly, each battery is expired
It fills, specifically, carrying out constant-current charge with the electric current of 0.5C, until voltage reaches 4.2V, progress is permanent after voltage reaches 4.2V
Pressure charging, until electric current reaches 0.05C.Then carry out overcharge test, detailed process is as follows: with 1C current versus cell into
Upper limit voltage is set as 12V by row constant-current charge, observes variation and the apparent condition of lithium ion battery temperature.Test result is such as
Shown in table 1.
Table 1: number is S1-S10 and the lithium ion battery of D1-D5 overcharges test result
| Number | Overcharge test phenomenon | Overcharge test battery maximum temperaturerise |
| S1 | Nothing is smoldered, without kindling | 130℃ |
| S2 | Nothing is smoldered, without kindling | 125℃ |
| S3 | Nothing is smoldered, without kindling | 120℃ |
| S4 | Nothing is smoldered, without kindling | 115℃ |
| S5 | Nothing is smoldered, without kindling | 110℃ |
| S6 | Nothing is smoldered, without kindling | 105℃ |
| S7 | Nothing is smoldered, without kindling | 100℃ |
| S8 | Nothing is smoldered, without kindling | 95℃ |
| S9 | Nothing is smoldered, without kindling | 90℃ |
| S10 | Nothing is smoldered, without kindling | 110℃ |
| D1 | It smolders | 320℃ |
| D2 | It smolders, catch fire | 400℃ |
| D3 | It smolders | 360℃ |
| D4 | It smolders, catch fire | 450℃ |
| D5 | It smolders, catch fire | 480℃ |
By the kindling it is found that battery S1~S10 does not smolder in overcharge of the test result of table 1, and use uncoated
Battery D1~D5 made of the positive electrode active materials of processing smolders or catches fire in overcharge；And battery S1~S10
Maximum temperaturerise is also significantly lower than battery D1~D5.It can be seen that using the lithium of the positive electrode with sensitive characteristic of the invention
When generation, which is abused or overcharged, causes temperature to increase, the resistance of the polythiofuran derivative sharply increases ion battery, to interrupt
Electric current prevents the generation for phenomena such as catching fire or exploding, to guarantee the security performance of battery.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist
Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (3)
1. a kind of preparation method of the electrode material with sensitive characteristic, which comprises the following steps:
Step 1: lithium metal oxide and polythiofuran derivative powder are weighed according to weight ratio, by polythiofuran derivative powder
It is dissolved in organic solvent, is then slowly added into lithium metal oxide, be sufficiently stirred, the speed of stirring is 1500 ~ 3000r/
Min obtains uniform dispersion；
Step 2: dispersion liquid is dried 2 ~ 6h at 100 ~ 160 DEG C, polythiofuran derivative is made to be evenly coated at lithium metal oxygen
Compound surface to get arrive the electrode material；
Wherein, the electrode material includes the core formed by the lithium metal oxide, and by the polythiofuran derivative shape
At shell, the weight proportion of the total electrode material of polythiofuran derivative Zhan is 0.1%~8%, the polythiofuran derivative
Curie temperature is 90 ~ 130 DEG C；The polythiofuran derivative be poly- 3- hexyl thiophene, poly- 3- heptyl thiophene, poly- 3- octyl thiophene,
Poly- 3- nonyl thiophene, poly- 3- decylthiophene, poly- 3- undecyl thiophene, poly- 3- dodecylthiophene, poly- 3- tridecyl thiophene
At least one of with poly- 3- myristyl thiophene；The lithium metal oxide is LiCoO2、LiNiO2、LiMn2O4、
LiaNibCocMndO2、LiaNibCocAldO2And LiFePO4At least one of, wherein 0.95≤a≤1.05,0 < b <
1,0 < c <, 1,0 < d < 1；The organic solvent is chloroform, tetrahydrofuran, any one or its in N-Methyl pyrrolidone
Combination.
2. the preparation method of the electrode material according to claim 1 with sensitive characteristic, it is characterised in that: described poly-
The weight proportion of the total electrode material of thiophene derivant Zhan is 1%~5%.
3. the preparation method of the electrode material according to claim 2 with sensitive characteristic, it is characterised in that: described poly-
The weight proportion of the total electrode material of thiophene derivant Zhan is 3%.
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| CN112345112B (en) * | 2020-10-21 | 2021-10-15 | 厦门大学 | Preparation method of temperature-sensitive nano probe |
| CN112467314A (en) * | 2020-11-03 | 2021-03-09 | 东莞市创明电池技术有限公司 | Thermosensitive material, electrode and preparation method thereof, and lithium secondary battery |
| CN112382746B (en) * | 2021-01-15 | 2021-04-23 | 湖南省正源储能材料与器件研究所 | Preparation method of lithium ion battery anode material with heat closing and self-healing functions |
| CN113690439A (en) * | 2021-07-27 | 2021-11-23 | 惠州锂威新能源科技有限公司 | Temperature-sensitive slurry, preparation method thereof, pole piece and secondary battery |
| CN114094281A (en) * | 2021-11-19 | 2022-02-25 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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| CN103534843A (en) * | 2012-05-07 | 2014-01-22 | 西奥公司 | Coated particles for lithium battery cathodes |
| CN106062032A (en) * | 2014-01-28 | 2016-10-26 | 株式会社理光 | Polythiophene derivative, method for producing same, positive electrode active material for secondary batteries, and secondary battery |
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| CN103534843A (en) * | 2012-05-07 | 2014-01-22 | 西奥公司 | Coated particles for lithium battery cathodes |
| CN106062032A (en) * | 2014-01-28 | 2016-10-26 | 株式会社理光 | Polythiophene derivative, method for producing same, positive electrode active material for secondary batteries, and secondary battery |
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