CN104603992B - Electrode for lithium ion secondary battery material, its manufacturing method and lithium rechargeable battery - Google Patents
Electrode for lithium ion secondary battery material, its manufacturing method and lithium rechargeable battery Download PDFInfo
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- CN104603992B CN104603992B CN201380045468.6A CN201380045468A CN104603992B CN 104603992 B CN104603992 B CN 104603992B CN 201380045468 A CN201380045468 A CN 201380045468A CN 104603992 B CN104603992 B CN 104603992B
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- 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
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- 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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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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- 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
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- H—ELECTRICITY
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- 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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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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 present invention provides electrode for lithium ion secondary battery material, its manufacturing method and the lithium rechargeable battery that can realize the lithium rechargeable battery that can maintain high current charge-discharge and high power capacity for a long time in the service life.In the electrode for lithium ion secondary battery material containing active material and conductive material, active material is set as lithium-contained composite oxide, tin-oxide or Si oxide, and contain amorphous carbon, carbon nanotube and carbon black as conductive material, part or all of the surface of active material is covered by amorphous carbon.
Description
Technical field
The present invention relates to electrode for lithium ion secondary battery material, its manufacturing method and lithium rechargeable batteries.In more detail
For, it is related to the high capacity technology of lithium rechargeable battery.
Background technology
The lithium rechargeable battery that cathode is formed using the material that can absorb and discharge lithium ion is formed with using lithium metal
The lithium battery of cathode is compared, and the precipitation of dendrite inhibition is capable of.Therefore, lithium rechargeable battery has the following advantages：Prevent battery
Short circuit and improve safety, and be capable of providing high power capacity and the high battery of energy density.
In recent years, which requires further high capacity, on the other hand, as power-supply system purposes
Battery, it is desirable that improve high rate during charging-discharging by reducing cell resistance.So, carried out below all the time
Effort：Lithium metal oxide positive electrode, the carbon-based negative electrode material high capacity of itself as cell reaction material, these are anti-
The small particle of material grains, the increase of long-pending, based on battery design the electrode area of specific grain surface are answered, and then passes through diaphragm
Be thinned and reduce liquid diffusion resistance etc..
However, these effort can incur as small particle, specific surface area increase caused by binder increase, therefore make
For as a result, high capacity is fallen back sometimes or positive/negative material is removed/fallen off from the metal foil as collector and occurs
Internal short-circuit of battery.In order to solve this problem, change binder type has been carried out to increase the research with the caking property of foil, has been somebody's turn to do
Although method can increase battery capacity, do not filled in terms of improving large current density electrical characteristics by reducing resistance
Point.
Therefore, existing lithium rechargeable battery is compared with the secondary cells such as nickel-cadmium cell, Ni-MH battery, large current density
Electrical characteristics are poor, this becomes larger performance penalty, it is difficult to electric tool, the Hybrid Vehicle for needing high current charge-discharge
It expands on the way.About the large current density electrification of the lithium rechargeable battery, for example, propose by using carbonaceous conductive material and
Realize the technology that electrode resistance reduces (for example, with reference to patent document 1).
On the other hand, in recent years, from the viewpoint of safety-sensitive and cost, just as lithium rechargeable battery
Pole material pays close attention to olivine-type LiFePO4 (LiFePO gradually4), but the resistance of the material is big, therefore low resistance becomes big
Problem (for example, with reference to patent document 2).So all the time, in order to solve low resistance possessed by olivine-type LiFePO4
The problem of change, has carried out that each of electrode material is made by olivine-type LiFePO4 and as the graphite Composite of conductive material
Kind research (for example, with reference to patent document 3,4).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-19399 bulletins
Patent document 2：Japanese Unexamined Patent Application Publication 2000-509193 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2002-75364 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2011-108522 bulletins
Invention content
Problems to be solved by the invention
However, when the charge and discharge cycles of high current are repeated in the lithium rechargeable battery described in patent document 1, due to
The dilation of positive/negative material and the conductive path for damaging particle between positive/negative, as a result, in the presence of nothing is become quickly
The problem of method circulation high current.On the other hand, for using the electrode material of olivine-type LiFePO4, pass through the compound of graphite
Change, the performance raising of electrode material, but olivine-type LiFePO4 are compared with other active materials, the capacity of per unit volume
It is small, therefore high capacity is certainly limited.
So it is a primary object of the present invention to providing can realize and can maintain large current density for a long time in the service life
Electrode for lithium ion secondary battery material, its manufacturing method and the lithium ion secondary of electricity and the lithium rechargeable battery of high power capacity
Battery.
The solution to the problem
The electrode for lithium ion secondary battery material of the present invention is the lithium ion secondary containing active material and conductive material
Electrode material for battery, abovementioned reactive species are lithium-contained composite oxide, tin-oxide or Si oxide, and aforesaid conductive material is
Amorphous carbon, carbon nanotube and carbon black, part or all of the surface of abovementioned reactive species are covered by aforementioned amorphous carbon.
Aforementioned amorphous carbon can for example be set as 10~95% to the coverage rate on abovementioned reactive species surface.
Aforementioned amorphous carbon can be the pyrolysate of organic matter.
When the electrode for lithium ion secondary battery material of the present invention is used for positive electrode, as abovementioned reactive species, example
It can such as use selected from by LiCoO2；LiMn2O4；LiNiO2；Li(MnaNibCoc)O2(wherein, a+b+c=1 and 0<a<1,0<b<
1,0<c<1)；Li(AldNieCof)O2(wherein, d+e+f=1 and 0<d<1,0<e<1,0<f<1)；xLi2MnO3-(1-x)LiMO2
(wherein, 0<x<And LiNi 1)gMn(2-g)O4(wherein, 0<g<2) a kind of lithium-contained composite oxide in the group formed.
When the electrode for lithium ion secondary battery material of the present invention is used for negative material, abovementioned reactive species for example can be with
Use Li4Ti5O12, the tin-oxide of interior packet metallic tin or the Si oxide of interior packet metallic silicon.
Alternatively, when the electrode for lithium ion secondary battery material of the present invention is used for negative material, abovementioned reactive species can
To use the mixture of the tin-oxide of graphite and interior packet metallic tin or the Si oxide of interior packet metallic silicon.
The manufacturing method of the electrode for lithium ion secondary battery material of the present invention is with the following process：By active material, lead to
It crosses thermal decomposition and forms the process that organic matter, carbon nanotube and the carbon black of amorphous carbon mix in a solvent；It will be by aforementioned mixed
It after mixture drying obtained from conjunction, is further heated, is formed on the surface of abovementioned reactive species and be originated from aforesaid organic substances
Amorphous carbon process；And the process for crushing the mixture after aforementioned heating.
The manufacturing method of another electrode for lithium ion secondary battery material of the present invention is with the following process：By active matter
The process that matter, carbon nanotube and carbon black mix in a solvent；After by the aforementioned mixture drying being obtained by mixing, further
The process heated；And the process for crushing the mixture after aforementioned heating, any one in foregoing carbon nanotubes and carbon black
Or both contain amorphous carbon.
The lithium rechargeable battery of the present invention uses aforementioned electrode for lithium ion secondary battery material.
The effect of invention
In accordance with the invention it is possible to realize the lithium ion that can maintain high current charge-discharge and high power capacity for a long time in the service life
Secondary cell.
Specific implementation mode
Hereinafter, mode for carrying out the present invention is described in detail.It should be noted that the present invention is not limited to
Embodiments described below.
(first embodiment)
It is illustrated firstly, for the electrode material of the first embodiment of the present invention.The electrode material of present embodiment
For lithium rechargeable battery, contain lithium-contained composite oxide, tin-oxide or Si oxide, and conduct as active material
Conductive material contains amorphous carbon, carbon nanotube and carbon black.In addition, in the electrode material of present embodiment, using as conduction
The amorphous carbon of material covers part or all of the surface of active material.
As a result, in the electrode material of present embodiment, amorphous carbon by cover active material surface by and active matter
Matter is electrically connected, and carbon nanotube makes them be electrically connected by being contacted with both amorphous carbon and carbon black.In turn, carbon black is whole in electrode
Conductive network is formed in body, and is electrically connected with collector.
[amorphous carbon]
Amorphous carbon as conductive material is low (degree of graphitization the is low) carbon of crystallinity, low by crystallinity, to
The surface of active material can be covered.On the other hand, high (degree of graphitization the is high) carbon of crystallinity has the distinctive stratiform of graphite
Structure, due to loosely being combined using Van der Waals force, layer is easy peeling-off in vertical direction each layer.Therefore, no
Suitable for covering the surface of active material.
When all surfaces of active material are set as 100%, the amorphous carbon is preferred to the coverage rate of active material surface
It is 10~95%, further preferably 20~95%.When coverage rate is less than 10%, active material and amorphous carbon are electrically connected with
When become inadequate.It is more advantageous to being electrically connected it should be noted that coverage rate is bigger, therefore the coverage rate of amorphous carbon can be with
Be 100%, but lithium ion when for charge and discharge to the intrusion of active material, from the disengaging of active material load hindered
The coverage rate of the heart, amorphous carbon is preferably set to 95% or less.
The amorphous carbon used in the electrode material of present embodiment is in addition to crystallinity low (degree of graphitization is low) without spy
It does not limit, is formed preferably by the pyrolysate of organic matter.Thereby, it is possible to make covering of the amorphous carbon to active material surface
It is in good condition.As the organic matter for forming amorphous carbon by thermal decomposition, such as glucose (C can be enumerated6H12O6), sucrose
(C12H22O11), dextrin ((C6H12O5)n), ascorbic acid (C6H8O6), carboxymethyl cellulose (CMC), polyvinylpyrrolidone
(PVP), polyallylamine hydrochlorides (PAH), polyacrylate (PAA), polyvinyl alcohol (PVA), silane coupling agent and coal tar pitch
(coal pitch) etc..
Using these organic matters active material surface formed amorphous carbon when, such as to by active material, carbon nanotube,
After the mixture that carbon black and organic matter are obtained by mixing in a solvent is dried, heated.
In addition, the inventors discovered that, when either or both of carbon nanotube and carbon black contain amorphous carbon, even if not making
With the organic matter for decomposing and being formed amorphous carbon, also active material surface can be covered well with amorphous carbon.At this point,
It is further heated after the mixture that active material, carbon nanotube and carbon black are obtained by mixing in a solvent is dried
.Carbon nanotube described herein containing amorphous carbon or carbon black are, for example,：With the amorphous of covering pipe body surfaces
Carbon nanotube of carbon-coating etc. (referring to Japanese Unexamined Patent Publication 2004-299986 bulletins).
[carbon nanotube]
The preferred fibre diameter of carbon nanotube as conductive material is 5~50nm and specific surface area is 50~400m2/g。
In the electrode material of present embodiment, carbon nanotube by with covering active material surface amorphous carbon in conjunction with by be electrically connected.
" in conjunction with " described herein also includes the combination based on covalent bond, Van der Waals force.
The reasons why carbon nanotube is combined with amorphous carbon can be lived with covering because carbon nanotube is fibrous particle
Property material surface amorphous carbon layer line contact.On the other hand, carbon black is spherical particle, therefore is only capable of connecing with amorphous carbon dots
It touches, cannot adequately combine.The method that amorphous carbon is combined with carbon nanotube is set to be not particularly limited, such as mentioned by adding
Heat make organic matter decompose and in the case where active material surface forms the method for amorphous carbon, the process that forms amorphous carbon
In, also it is formed simultaneously the combination of amorphous carbon and carbon nanotube.
In addition, in the electrode material of present embodiment, carbon nanotube by with carbon black in conjunction with by be electrically connected.By carbon nanotube
The method combined with carbon black is not particularly limited, such as has the following method：When manufacturing carbon black by so that hydrocarbon is thermally decomposed, import
The method that carbon nanotube is combined；In the thermal decomposition of acetylene gas and/or in the state of so that acetylene gas is thermally decomposed, supply
To the hydrocarbon for including carbon nanotube formation catalyst, the method that is combined (referring to Japanese Unexamined Patent Application Publication 2009-503182 bulletins)；
Carbonized stock liquid in carbon nanotube and carbon black dispersion to the carbonized stocks liquid such as hydrocarbon, alcohol, will be made to lead in the state of liquid or gasification
It crosses the operation such as heating and is carbonized, the method being combined each other；By using the gimmick of the mechanochemistry of solid dielectric
The method etc. that carbon nanotube and carbon black are combined.
The method for combining carbon nanotube and carbon black as the gimmick by mechanochemistry has using ball mill, vibration
The method of the media stirred type mixing machine such as grinding machine and ball mill.At this point, for example by active material, decomposing to form amorphous carbon
Organic matter, carbon nanotube and carbon black when mixing in a solvent, or by active material, either or both contain amorphous carbon
When carbon nanotube and carbon black mix in a solvent, the gimmick of mechanochemistry can be used to be combined carbon nanotube with carbon black, also may be used
To be combined when heating upon mixing.
[carbon black]
Carbon black as conductive material is preferably acetylene black or furnace black, may further preferably be made to battery performance
At the less acetylene black of the impurity content of influence.In addition, the specific surface area of carbon black is less than the specific surface area of carbon nanotube, and it is
10~200m2/ g is preferred.In turn, specified in the JIS K 1469 of the carbon black used in the electrode material of present embodiment
Ash content is preferably 1.0 mass % or less.
In the electrode material of present embodiment, as previously mentioned, carbon black not only with carbon nanotube in conjunction with and be electrically connected, Er Qie
Conductive network is formed in electrode entirety, and is electrically connected with collector.Carbon black can form conductive network in electrode entirety
Reason is because carbon black is different from carbon nanotube, is spherical particle, favorable dispersibility, therefore easy is integrally divided throughout electrode
Cloth.In addition, carbon black is because having spherical primary particle to connect into the reasons why being electrically connected with carbon nanotube, collector
The unique high-order structures of chain, regardless of whether being spherical particle conducting all easy to implement.
[active material]
The active material of the electrode material of present embodiment is lithium-contained composite oxide, tin-oxide or Si oxide.Example
When such as using the electrode material of present embodiment as positive electrode, LiCoO can be used2、LiMn2O4、LiNiO2、Li
(MnaNibCoc)O2(wherein, a+b+c=1 and 0<a<1,0<b<1,0<c<1)、Li(AldNieCof)O2(wherein, d+e+f=1 and 0
<d<1,0<e<1,0<f<1)、xLi2MnO3-(1-x)LiMO2(wherein, 0<x<And LiNi 1)gMn(2-g)O4(wherein, 0<g<2)
The positive active material of equal oxides system.
When on the other hand, using the electrode material of present embodiment as negative material, active material can use
Li4Ti5O12, interior packet metallic tin tin-oxide and Nei Bao metallic silicons Si oxide etc..In addition, as negative electrode active material,
It can also material made of admixed graphite in the tin-oxide of packet metallic tin or the Si oxide of interior packet metallic silicon including use.
It should be noted that LiFePO4(olivine-type LiFePO4), LiMnPO4、LiMnXFe(1-X)PO4Deng phosphoric acid containing lithium
Battery capacity of the salt due to being substantially difficult to improve per unit volume, is unsuitable for the activity of the electrode material of present embodiment
Substance.
[manufacturing method]
The manufacturing method of the electrode material of present embodiment is not particularly limited, such as can be by carrying out following process
Manufacture：Form what organic matter, carbon nanotube and the carbon black of amorphous carbon mixed in a solvent by active material, by thermal decomposition
Process；It after being dried by the mixture being obtained by mixing, is further heated, being formed to be originated from the surface of active material has
The process of the amorphous carbon of machine object；And the process for crushing the mixture after heating.When being manufactured by this method, it is preferable to use
It is easy to be dissolved in solvent and decomposes and formed the organic matter of amorphous carbon when heated.
In addition, the electrode material of present embodiment can also be manufactured by carrying out following process：Using in carbon nanotube
With the material containing amorphous carbon in either or both of carbon black, active material, carbon nanotube and carbon black are mixed in a solvent
The process of conjunction；After by the drying of the mixture that is obtained by mixing, the process that is further heated；And it will be mixed after heating
Close the process that object crushes.
Mixed processes in aforementioned each manufacturing method can use mixing and kneading machine, universal mixer, Henschel mixer or band
The media stirred type mixing machines such as the mixing machines such as formula mixing machine or ball mill, vibrating mill or ball mill carry out.In addition, mixing
The solvent used in process can be water, but in order to improve the dispersibility of carbon nanotube, carbon black, the mixing of preferably water and alcohol is molten
The nonaqueous solvents such as agent, alcohol.
Active material is the tin-oxide of interior packet metallic tin or the Si oxide of interior packet metallic silicon and then is mixed in them
Made of graphite when material, for the solvent of mixed processes, in order to prevent metallic tin, metallic silicon hydrolysis or improve graphite
Dispersibility is, it is preferable to use the nonaqueous solvents such as alcohol.
In addition, after mixed processes, by drying obtained mixture, to remove solvent.The drying side of mixture
Method is not particularly limited, when using the organic matter for forming amorphous carbon by thermal decomposition, if being filtered, it should be noted that not
By organic matter be removed in the form of filtrate together with solvent.So in the drying of mixture, in addition to filtering, may be used also
With application be freeze-dried, be dried under reduced pressure, be dried in vacuo or vibrating flowing dry the methods of.
After the drying or and then it dries, heats mixture.Use the organic matter that amorphous carbon is formed by thermal decomposition
When, amorphous carbon, and the surface of amorphous carbon covering active material are formed from organic matter by heating, and then formed without fixed
The combination of shape carbon and carbon nanotube, the combination of carbon nanotube and carbon black.In addition, using the carbon nanotube containing amorphous carbon, containing
When having the carbon black of amorphous carbon, the surface of amorphous carbon covering active material contained in carbon nanotube and/or carbon black, and shape
At the combination of the combination of amorphous carbon and carbon nanotube, carbon nanotube and carbon black.
The conditions such as temperature, atmosphere when heating mixture are different according to used active material.Carbon system in order to prevent
The oxidation of material, atmosphere are preferably inert atmosphere or reducing atmosphere.In addition, active material uses LiCoO2、LiMn2O4、
LiNiO2、Li(MnaNibCoc)O2(wherein, a+b+c=1 and 0<a<1,0<b<1,0<c<1)、Li(AldNieCof)O2(wherein, d+
E+f=1 and 0<d<1,0<e<1,0<f<1)、xLi2MnO3-(1-x)LiMO2(wherein, 0<x<And LiNi 1)gMn(2-g)O4(its
In, 0<g<Etc. 2) when the positive active material of oxides system, the reduction decomposition of active material itself in order to prevent, it is preferred to use dry
The oxidizing atmospheres such as dry air.When in turn, using the organic matter for forming amorphous carbon by thermal decomposition, preferably compared with low temperature
It is heated at 200~400 DEG C so that these organic matters are decomposed without burning.
On the other hand, used as the Li of negative electrode active material4Ti5O12When, due to Li4Ti5O12It is not easily decomposed, therefore excellent
It is selected at slightly higher 300~500 DEG C and heats.In addition, active material using interior packet metallic tin tin-oxide or mix wherein
Made of graphite when material, it will not be decomposed the active material in inert atmosphere or reducing atmosphere, therefore can use
The non-active gas such as argon gas, nitrogen, since the fusing point of metallic tin is 232 DEG C of low temperature, preferably in the temperature less than 232 DEG C
Lower heating.
Active material is for the Si oxide of interior packet metallic silicon or wherein made of admixed graphite when material, even if non-live
Property atmosphere or reducing atmosphere in active material will not decompose, can be with and since the fusing point of silicon is 1410 DEG C of high temperature
It is heated within the scope of the wider temperature near 1400 DEG C, and then the non-active gas such as argon gas, nitrogen can be used.Heating
Mixture afterwards makes aggregation loosen by crushing, to obtain the electrode material of present embodiment.
About the electrode material of present embodiment, the electronics conducting networks in electrode improve, and active material, conductive agent
Giving and accepting for electronics between the collector of metal foil is smoothed out, therefore is made with existing each electrode material is merely mixed
The electrode material made is compared, and electrode resistance is reduced, and high current charge-discharge is possibly realized.In addition, the electrode material of present embodiment
Material optimizes the electrical connection between the collector of active material, conductive agent and metal foil, and a small amount of conductive agent realization can be utilized to lead
It is logical, therefore especially become apparent with the performance difference of existing electrode material in a small amount of use.Furthermore it is possible to use on a small quantity
Degree to improve battery capacity contribution it is big.
As a result, by using the electrode material of present embodiment, the ratio of the active material in electrode material can be improved,
Make lithium rechargeable battery high capacity.
(second embodiment)
Then, the lithium rechargeable battery of second embodiment of the present invention is illustrated.The lithium of present embodiment
Ion secondary battery has used the electrode material of foregoing first embodiment in aforementioned positive electrode material and/or negative material.
Common lithium rechargeable battery is made of the electrolyte of electrode group and the dipping electrode group, and the electrode group passes through
Electrode including cathode and anode is clipped membrane layer to fold or wind and formed.Electrode is by by electrode for lithium ion secondary battery
Material is coated on the collector of metal foil by organic binder etc. and is formed.
When using electrode of the electrode material of foregoing first embodiment to form lithium rechargeable battery, by electrode material
It is kneaded with solvent, binder, forms electrode composition (slurry).Such as when forming anode, N- methyl pyrroles can be used as solvent
Pyrrolidone (NMP) can use Kynoar (PVDF) as binder.In addition, when forming cathode, usually as solvent
Using water, carboxymethyl cellulose (CMC) and SBR styrene butadiene rubbers (SBR) are used as binder.
Then, after electrode composition being coated on the collector of metal foil, electrode can be made by press molding.
Active material is LiCoO2、LiMn2O4、LiNiO2、Li(MnaNibCoc)O2(wherein, a+b+c=1 and 0<a<1,0<b<1,0<c<
1)、Li(AldNieCof)O2(wherein, d+e+f=1 and 0<d<1,0<e<1,0<f<1)、xLi2MnO3-(1-x)LiMO2(wherein, 0
<x<And LiNi 1)gMn(2-g)O4(wherein, 0<g<2) positive active material of oxides system or as negative electrode active material such as
Li4Ti5O12When, collector can use aluminium foil.In addition, active material is the tin-oxide of interior packet metallic tin or interior category covered with gold leaf
The Si oxide of silicon made of admixed graphite when material, can use copper foil in them.
As the other materials used in lithium rechargeable battery, diaphragm, electrolyte etc. can be enumerated.Diaphragm is for making just
Pole and cathode are electrically insulated and keep electrolyte, can use the plastic diaphragms such as polyethylene, polypropylene, cellulose system without
Woven fabric.In order to improve the retentivity of electrolyte, it is preferable to use the diaphragms of porous film shape for diaphragm.
In addition, the electrolyte as aforementioned impregnation electrode group passes, it is preferable to use wrapping nonaqueous electrolytic solution or ion containing lithium salt
Lead polymer etc..As the nonaqueous solvents for wrapping the nonaqueous electrolyte in nonaqueous electrolytic solution containing lithium salt, ethylene carbonate can be enumerated
Ester (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC) etc..In addition,
As the lithium salts that can be dissolved in nonaqueous solvents, lithium hexafluoro phosphate (LiPF can be enumerated6), LiBF4 (LiBF4), trifluoro
Methanesulfonic acid lithium (LiSO3CF3) etc..
The lithium rechargeable battery of present embodiment has used the electrode material of foregoing first embodiment, therefore can be
High current charge-discharge is maintained in service life for a long time, and there is high power capacity.
Embodiment
Hereinafter, enumerating examples and comparative examples of the present invention, the effect of the present invention is specifically described.About this
Embodiment makes electrode material by method described below, evaluates its performance.
<Examples 1 to 8>
Using mixing machine, in a solvent by active material, organic matter, carbon nanotube and carbon black etc. shown in following table 1
Mixing.Then, by being dried, heating, crush, to obtain the electrode material of Examples 1 to 8.It is shown in following table 2 each
Condition in process.
<Embodiment 9>
By manganese nitrate (Mn (NO3)2·6H2O), nickel nitrate (Ni (NO3)2·6H2) and cobalt nitrate (Co (NO O3)2·6H2O)
According to molar ratio computing Mn:Ni:Co=4:1:1 ratio is added in distilled water, makes it dissolve.Then, in nitrogen atmosphere
According to molar ratio computing Li2CO3:(Mn+Ni+Co)=1.75:1 ratio addition lithium carbonate (Li2CO3), after being sufficiently stirred, into
Row filtering, cleaning, drying, to obtain powder.
By it in an atmosphere, roasted 4 hours at 500 DEG C after, roasted 10 hours at 900 DEG C, to obtain black powder.
For obtained powder, elemental analysis and X-ray diffraction measure are carried out, as a result it is with 0.5Li2MnO3-0.5LiMn1/ 3Ni1/3Co1/3O2Composition compound.
Then, by the embodiment 1 of Japanese Unexamined Patent Publication 2004-299986 bulletins described in method, obtain surface by nothing
The carbon nanotube of amorphous carbon layer covering.It is mixed in a solvent with aforementioned black powder and carbon black using mixing machine.Then, lead to
It crosses and is dried, heats, crushing, to obtain the electrode material of embodiment 9.Used each material is shown in following table 1.Separately
Outside, the condition in each process is shown in following table 2.
<Embodiment 10>
By nickel chloride (NiCl2·6H2) and manganese chloride (MnCl O2·4H2O) according to molar ratio computing Ni:Mn=1:3 side
After formula mixing, according to molar ratio computing (Ni+Mn):C2O4=5:Ammonium oxalate ((NH is added in 6 mode4)2C2O4·H2O it) and mixes
It closes.After mixture is dried 2 hours at 110 DEG C, roast 4 hours in an atmosphere, at 400 DEG C.
Then, according to molar ratio computing Li:(Ni+Mn)=1:Lithium carbonate (Li is added in 2 mode2CO3) and mix, in turn
In an atmosphere, it roasts 48 hours at 700 DEG C, to obtain black powder.For obtained powder, carries out elemental analysis and X is penetrated
Line diffraction, as a result it is with LiNi0.5Mn1.5O4Composition compound.
Then, by the embodiment 1 of Japanese Unexamined Patent Publication 2004-299986 bulletins described in method, obtain surface by nothing
The carbon nanotube of amorphous carbon layer covering.It is mixed in a solvent with aforementioned black powder and carbon black using mixing machine.Then, lead to
It crosses and is dried, heats, crushing, to obtain the electrode material of embodiment 10.Used each material is shown in following table 1,
Condition in each process is shown in following table 2.
[table 1]
[table 2]
Electrode material for the Examples 1 to 10 manufactured by preceding method uses scanning electron microscope (Japan
Electronics Co., Ltd manufactures JSM-7400F) shooting reflective electron composition image, measure covering of the amorphous carbon to active material
Rate.In addition, using transmission electron microscope (Jeol Ltd.'s manufacture JEM-2010), Examples 1 to 10 is shot
Transmission electron beam (TEM) image of electrode material, confirm the presence or absence of combination of amorphous carbon and carbon nanotube and carbon nanotube and
The presence or absence of combination of carbon black.It the results are shown in following Table 3.
[table 3]
As shown in Table 3 above, the amorphous carbon coverage rate of the electrode material of Examples 1 to 10 is 10% or more.In addition, real
Apply example 1~10 electrode material confirm the combination of amorphous carbon and carbon nanotube, the combination of carbon nanotube and carbon black and
The formation of conductive network based on carbon black.
<Embodiment 11~20>
Then, electrode (anode/cathode) is formed using the electrode material of Examples 1 to 10, makes embodiment 11~20
Lithium rechargeable battery.Specifically, by the electrode material of Examples 1 to 10 and as the Kynoar of binder
(Kureha Corporation manufacture KF polymer solutions) is according to by quality ratio 95:5 ratio compounding.Addition is made wherein
For the N-Methyl pyrrolidone (Sigma-Aldrich corporations moulding number 328634) of dispersion solvent, kneading machine (PRIMIX is used
Corporation manufacture HIVIS MIX and HOMODISPER) it is kneaded, to make electrode composition (slurry).
The electrode composition (slurry) is applied on the aluminium foil or copper foil of 20 μm of thickness and is dried, then, is pressed
System, cuts into 40mm square, to obtain electrode of lithium secondary cell.Diaphragm for being electrically isolated them uses 50mm square
Olefin(e) fibre non-woven fabrics.Electrolyte use is by EC (Aldrich manufacture ethylene carbonate) and MEC, (Aldrich is public
Department's manufacture methyl ethyl carbonate) according to volume basis 30:1mol/L hexafluorophosphoric acids are dissolved in the solution that 70 ratio mixes
(Stella Chemifa Corporation manufacture LiPF to lithium6) obtained from electrolyte.
Use following negative electrode：Relative to a part of cathode electrode material, negative electrode active material uses graphite
(Osaka Gas Co., Ltd.s manufacture artificial graphite MCMB6-28), (electrochemically with the acetylene black as conductive material by it
Industrial Co., Ltd manufactures HS-100) and Kynoar as binder according to by quality ratio 95:1:4 ratio is mixed
It closes.Then, slurry is made in the same manner as former electrodes material, is applied on the copper foil of 20 μm of thickness, is dried, then, into
Row compacting, cuts into 40mm square, the negative electrode obtained from.It, will be whole enclosed on anode and cathode after connection terminal
Into aluminium laminate packaging body, the laminated-type battery of 70mm square is made.
In addition, a part for electrode made of being coated and dried and then suppress on aluminium foil or copper foil is not used for battery, and
It is to observe electrode surface using scanning electron microscope, confirms carbon black using obtained scanning beam (SEM) image and exist
Conductive network is formd in electrode entirety.These results are shown in above-mentioned table 3.Any electrode surface confirms in Examples 1 to 10
To the formation of the conductive network based on carbon black, therefore speculate that the electrode back side contacted with the metal foil as collector is also formed together
The conductive network of sample and be electrically connected with collector.
<Comparative example 1~10>
Using active material same as previous embodiment 1~10, carbon nanotube and carbon black, makes in following table 4 and show
Comparative example 1~10 electrode material.The electrode material of comparative example 1~10 is directly according to binder by quality ratio:Its remaining part
Divide=5:95 ratio is compounded into the Kynoar as binder, and (Kureha Corporation manufacture KF polymer is molten
Liquid) in, N-Methyl pyrrolidone of the addition as dispersion solvent, is kneaded using kneading machine, to make electrode wherein
Mixture (slurry).
Wherein, in comparative example 1~8, it is not added with the organic matter for decomposing and being formed amorphous carbon, alternatively, in reality
It applies and is further added to what the when of being decomposed with the organic matter used in Examples 1 to 8 was generated on the basis of the amounts of carbon black of example 1~8
Carbon amounts is same amount of carbon black.By the type of active material, carbon nanotube and carbon black in the electrode material of comparative example 1~10 and
Compounding amount is shown in following table 4 together.
[table 4]
<Embodiment 21~22>
It, from other than 3g is changed to 0.3g, is operated similarly to Example 1, to make in addition to by the amount of the sucrose in embodiment 1
Make the electrode material of embodiment 21.Specifically, forming having for amorphous carbon by conductive agent, by thermal decomposition using mixing machine
It after machine object, carbon nanotube and carbon black mix in a solvent, is dried, heats, crushes, to obtain the electrode material of embodiment 21
Material.
The obtained embodiment of the reflective electron composition determining image that is obtained by using scanning electron microscope 21
The amorphous carbon of electrode material is to the coverage rate of active material, result 5%.In addition, by using transmission electron microscope
Transmission electron beam (TEM) image that (Jeol Ltd.'s manufacture JEM-2010) is obtained confirms amorphous carbon and carbon nanometer
The presence or absence of the combination of the presence or absence of combination of pipe and carbon nanotube and carbon black, although as a result observing the knot of carbon nanotube and carbon black
It closes, but the combination of amorphous carbon and carbon nanotube is not observed.
Then, for the electrode material of embodiment 21, it is compounded the polyvinylidene fluoride as binder similarly to Example 10
Alkene is added the N-Methyl pyrrolidone as dispersion solvent, is kneaded using kneading machine, to make electrode composition (slurry
Material).And then electrode is used it for, make the laminated-type battery of embodiment 22.
<Comparative example 13~22>
Other than the electrode composition that will be made in comparative example 1~10 is for electrode, respectively almost with embodiment 11~20
It similarly operates, to the laminated-type battery of comparison example 13~22.
[discharge performance evaluation]
Then, for the lithium ion secondary of the embodiment 11~20,22 and comparative example 13~22 that are made by preceding method
Battery (laminated-type battery) carries out discharge performance experiment.Specifically, by after each battery primary charging, confirm that efficiency for charge-discharge reaches
To near 100%, measure with 0.7mA/cm2Current density carry out constant current discharge to 2.7V (embodiment 12,15,17 and ratio
Be 1.2V compared with example 14,17,19, embodiment 20 and comparative example 22 are 3.0V) when discharge capacity.It will the charge and discharge in 1 hour
The current value of the capacity (mAh) is denoted as " 1C ".
After first charge and discharge, charging carries out that (embodiment 12,15,17 and comparative example 14,17,19 are 2.8V, are implemented to 4.3V
Example 19 and comparative example 21 are 4.8V, and embodiment 20 and comparative example 22 are 5.0V) when 0.05C electric currents (0.2C constant currents, terminate), it puts
With 0.2C, 0.33C, 0.5C, 1C, 3C, 5C, 10C, (constant current, when 2.7V terminates electricity, embodiment 12,15,17 in each cycle
With comparative example 14,17,19 to terminate when 1.2V, embodiment 20 and comparative example 22 terminate when being 3.0V) it is slowly increased current value, temporarily
It is parked between charge and discharge and carries out 10 minutes, so carry out charge and discharge, it will be relative to the charge and discharge of the charge/discharge capacity of first (0.2C)
The ratio (%) of capacitance is denoted as speed characteristic.I-V characteristic when in turn, using SOC (depth of charge) 50% calculates the straight of battery
Leakage resistance (DCR).It is denoted as when D.C. resistance when charging is denoted as " charging DCR ", electric discharge " electric discharge DCR ".By these results one
And it is shown in following table 5.
[table 5]
As shown in Table 5 above, the lithium ion secondary electricity of the embodiment 11~20 of the electrode material of Examples 1 to 10 has been used
Pond with embodiment 22, comparative example 13~22 lithium secondary battery compared with, battery cell capacity is big, in addition, be charged and discharged in
D.C. resistance is also low, and discharge performance is also excellent.It is confirmed by the result, in accordance with the invention it is possible to realize when can be long in the service life
Between maintain the lithium rechargeable battery of high current charge-discharge and high power capacity.
Claims (9)
1. a kind of electrode for lithium ion secondary battery material is the lithium rechargeable battery containing active material and conductive material
With electrode material,
The active material be lithium-contained composite oxide, tin-oxide or Si oxide,
The conductive material be amorphous carbon, carbon nanotube and carbon black,
Wherein, the fibre diameter of the carbon nanotube is 5~50nm and specific surface area is 50~400m2/ g, the ratio of the carbon black
Surface area is less than the specific surface area of the carbon nanotube, and is 10~200m2/ g,
Part or all of the surface of the active material is covered by the amorphous carbon,
The active material is Li4Ti5O12, the tin-oxide of interior packet metallic tin or the Si oxide of interior packet metallic silicon, and the lithium
Ion secondary battery is used for negative material with electrode material,
The electrode for lithium ion secondary battery material is manufactured by manufacturing method with the following process：
Form what organic matter, carbon nanotube and the carbon black of amorphous carbon mixed in a solvent by active material, by thermal decomposition
Process；
After by the mixture drying being obtained by mixing, further heated, in the surface shape of the active material
At the process of the amorphous carbon from the organic matter；And
The process that mixture after the heating is crushed.
2. electrode for lithium ion secondary battery material according to claim 1, wherein the amorphous carbon is to the activity
The coverage rate of material surface is 10~95%.
3. electrode for lithium ion secondary battery material according to claim 1, wherein the active material be graphite with it is interior
The mixture of the Si oxide of the tin-oxide of packet metallic tin or interior packet metallic silicon,
The electrode for lithium ion secondary battery material is used for negative material.
4. electrode for lithium ion secondary battery material according to claim 2, wherein the active material be graphite with it is interior
The mixture of the Si oxide of the tin-oxide of packet metallic tin or interior packet metallic silicon,
The electrode for lithium ion secondary battery material is used for negative material.
5. a kind of electrode for lithium ion secondary battery material is the lithium rechargeable battery containing active material and conductive material
With electrode material,
The active material be lithium-contained composite oxide, tin-oxide or Si oxide,
The conductive material be amorphous carbon, carbon nanotube and carbon black,
Wherein, the fibre diameter of the carbon nanotube is 5~50nm and specific surface area is 50~400m2/ g, the ratio of the carbon black
Surface area is less than the specific surface area of the carbon nanotube, and is 10~200m2/ g,
Part or all of the surface of the active material is covered by the amorphous carbon,
The active material is Li4Ti5O12, the tin-oxide of interior packet metallic tin or the Si oxide of interior packet metallic silicon, and the lithium
Ion secondary battery is used for negative material with electrode material,
The electrode for lithium ion secondary battery material is manufactured by manufacturing method with the following process：
The process that active material, carbon nanotube and carbon black are mixed in a solvent；
After the mixture drying being obtained by mixing by described, the process that is further heated；And
The process that mixture after the heating is crushed,
Either or both of the carbon nanotube and carbon black contain amorphous carbon.
6. electrode for lithium ion secondary battery material according to claim 5, wherein the amorphous carbon is to the activity
The coverage rate of material surface is 10~95%.
7. electrode for lithium ion secondary battery material according to claim 5, wherein the active material be graphite with it is interior
The mixture of the Si oxide of the tin-oxide of packet metallic tin or interior packet metallic silicon,
The electrode for lithium ion secondary battery material is used for negative material.
8. electrode for lithium ion secondary battery material according to claim 6, wherein the active material be graphite with it is interior
The mixture of the Si oxide of the tin-oxide of packet metallic tin or interior packet metallic silicon,
The electrode for lithium ion secondary battery material is used for negative material.
9. a kind of lithium rechargeable battery uses the electrode material described in any one of claim 1~8.
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| JP2015191688A (en) * | 2014-03-27 | 2015-11-02 | 三菱マテリアル株式会社 | Negative-electrode active material for lithium ion secondary battery and manufacturing method for the same |
| US9550907B2 (en) * | 2015-02-27 | 2017-01-24 | Gates Corporation | Carbon nanostructure preblends and their applications |
| JP6965991B2 (en) * | 2017-07-20 | 2021-11-10 | 日本電気株式会社 | Carbon Conductive Additive for Lithium Ion Batteries |
| WO2019073830A1 (en) * | 2017-10-10 | 2019-04-18 | デンカ株式会社 | Positive electrode composition for lithium ion secondary batteries, positive electrode for lithium ion secondary batteries, and lithium ion secondary battery |
| EP4152440A3 (en) * | 2017-12-01 | 2023-04-26 | LG Energy Solution, Ltd. | Negative electrode and secondary battery including the same |
| KR20200094428A (en) * | 2019-01-30 | 2020-08-07 | 에스케이이노베이션 주식회사 | Secondary Battery and the Fabrication Method Thereof |
| KR102244226B1 (en) * | 2019-10-22 | 2021-04-26 | 주식회사 그랩실 | Silicon Composite Anode Active Material including Network of Conductive Fibers, Manufacturing method thereof and Lithium Secondary Battery Comprising the Same |
| KR20210153997A (en) | 2020-06-11 | 2021-12-20 | 주식회사 엘지에너지솔루션 | Negative electrode and secondary battery comprising the same |
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| JP3992708B2 (en) * | 2003-10-31 | 2007-10-17 | 日立マクセル株式会社 | Non-aqueous secondary battery electrode material, method for producing the same, and non-aqueous secondary battery using the same |
| KR100796687B1 (en) * | 2005-11-30 | 2008-01-21 | 삼성에스디아이 주식회사 | Active material for rechargeable lithium battery, method of preparing thereof and rechargeable lithium battery comprising same |
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