CN107256960A - A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole - Google Patents
A kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole Download PDFInfo
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Abstract
The present invention relates to technical field of lithium batteries, a kind of composite positive pole, its preparation method and the lithium ion battery comprising the composite positive pole, the composite positive pole, including following material are disclosed：Modified polyorganosiloxane and LiCo1‑xMxPO4/C；The M is at least one of Fe, Mn, Ni, Zn, Mo, Ti, Mg；The present invention is by by LiCo1‑xMxPO4With the compound skeleton containing loose structure, the volumetric expansion that electrode material is produced in charge and discharge process can be effectively improved, while improving the coulombic efficiency and cyclical stability of battery, passes through modified polyorganosiloxane and LiCo1‑xMxPO4/ C is combined, and corrosiveness of the electrolyte to positive electrode is reduced, so as to improve the stability and cycle life of battery.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to composite positive pole and preparation method thereof and compound comprising this
The lithium ion battery of positive electrode.
Background technology
In recent years, because environmental pollution and energy doctor are weary, each state is all striving to find new environmental protection sustainable development
The energy.Lithium battery is that versatility is most strong so far, adaptability most wide secondary cell, with energy density is high, the circulation longevity
The advantages of life is long, operating voltage is high.
The capacity of positive electrode directly determines the capacity of lithium battery, therefore it is good with one kind to find a kind of good positive electrode
Synthetic method directly affects the development trend of lithium battery.Anode material of lithium battery is typically all the oxide of lithium, current city
The positive electrode of fieldization mainly has LiFePO4 of cobalt acid lithium, the LiMn2O4 of spinel structure and olivine structural etc., wherein cobalt
The major advantage of sour lithium is high electrical conductivity, simple production process and easily preparation etc., but its preparation cost is higher, environmental pollution
The larger development for but constraining it.LiMn2O4 has spinel structure, and its major advantage is cheap, safe, ratio
It is easier to prepare, has the disadvantage that theoretical capacity is high, high-temperature behavior is poor.LiFePO 4 material is the popular positive pole of Recent study
One of material, it has the advantages that high stability, safer, more environmentally friendly and cheap, has the disadvantage energy density and room temperature
Electrical conductivity is relatively low, and the less stable of metal oxide cathode material, after long-time discharge and recharge, and the capacity of battery can be sent out
Life is significantly reduced, and electrolyte can be leaked, and corrosion is caused to positive electrode, its service life is influenceed, thus more and more not
People couple can be met while the demand of high power capacity, high-energy-density electronic product and longer service life.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of composite positive pole, and it has
There is the characteristics of capacity is high, stability is good, service life is long.
The second purpose of invention is to provide a kind of preparation method of composite positive pole.
The fourth purpose of invention is to provide a kind of lithium battery.
To achieve these goals, the present invention provides a kind of composite positive pole, including following material：Modified polyorganosiloxane
And LiCo1-xMxPO4/C；
The M is at least one of Fe, Mn, Ni, Zn, Mo, Ti, Mg.
The present invention is by modified polyorganosiloxane in LiCo1-xMxPO4/ C Surface formation diaphragm, can ooze in electrolyte
During leakage, prevent electrolyte from corroding to positive active material, cause the inactivation of active material, so as to influence the use longevity of battery
Life.
In composite positive pole, the influence of the content of each material to its capacity and service life is very big, works as LiCo1- xMxPO4When/C content is too low, then the capacity of battery can be caused to reduce, cyclical stability is deteriorated, and when modified polyorganosiloxane
When content is too low, then it can not be to LiCo1-xMxPO4/ C is effectively coated, it is impossible to effectively protect LiCo1-xMxPO4/C.It is excellent
Choosing, described composite positive pole includes the material of following parts by weight：LiCo1-xMxPO4The parts by weight of/C 92~98, modification are poly-
The parts by weight of siloxanes 2~8.
The surface tension of modified polyorganosiloxane is small, the characteristic with lyophoby, and it is difficult to adsorb in positive electrode to make electrolyte
Surface, so as to reduce corrosion of the electrolyte to positive electrode, the modified polyorganosiloxane is poly- tetramethyl tetravinyl ring silica
Alkane, poly- diphenyldimethyl siloxanes, PSI grafting dimethyl siloxane and poly- N, N- diphenyltetramethyl
At least one of ring disiloxane.
The present invention also provides a kind of preparation method of composite positive pole, comprises the following steps：
(1) cobalt source and ligand reaction are generated into metal complex, then metal complex is mixed with gelator in a solvent
Close uniform, ageing obtains plural gel；
(2) plural gel is calcined into 3.5~4.5h in inert gas, calcining heat is 350~420 DEG C, is calcined
Product；
(3) lithium source, ferrophosphorus source, cobalt source, M sources and calcined product are subjected to hydro-thermal reaction in aqueous, obtain LiCo1- xMxPO4/C；
(4) by LiCo1-xMxPO4After/C, modified polyorganosiloxane are mixed in proportion, composite positive pole is obtained；
Wherein, the M is at least one of Fe, Mn, Ni, Zn, Mo, Ti, Mg.
In step (1), the chemical reaction such as gelator can be hydrolyzed, is condensed in a solvent, and form stable
Sol system, colloidal sol is aged, slowly polymerize between micelle, forms the gel of three-dimensional space network structure, gel after drying,
The solvent molecule between three-dimensional space network can be sloughed, then through calcining, removes the hydrogen in organic matter, then forms to have and well leads
Electrical three-dimensional carbon skeleton, by the way that metal complex is combined with organogel, can in three-dimensional carbon skeleton doping metals it is former
Son, improves the surface-active and conductance of carbon skeleton.The structure of three-dimensional carbon skeleton can change according to the change of the species of gel,
It is preferred that, the organogel factor is cyclodextrine derivatives, cholesteryl anthraquinone-2-carboxylic acid, benzyl carbamide derivative, 2- pungent
Base dodecyl 4- [(naphthalidine) carboxyl amine] benzoic ether, 1,4- bis- [(the octyloxy benzene of 3,4- bis-)-connection amide groups] benzene, N-
(3,4- alkoxybenzoyls)-N '-(4 '-nitro benzoyl) hydrazine, N- (3,5- alkoxybenzoyls)-N '-(4 '-cyanogen
At least one of base benzoyl) hydrazine.
The driving force of the aggregation of gelator and banking process derives from the phase between intermolecular polarity group in organic solvent
Interaction, therefore the species of solvent is to influence the key factor of gel form, or even can determine that gel can be generated, the present invention
In, the organic solvent is at least one of n-butanol, ethanol, 1-METHYLPYRROLIDONE, acetone etc..
Three-dimensional carbon skeleton can be effectively improved the volumetric expansion that electrode material is produced in charge and discharge process, and hole can also be
The migration of electronics and ion provides passage, and its larger specific surface area can be LiCo1-xMxPO4Attachment point is provided, improved
LiCo1-xMxPO4Load capacity, reduce the loss that is caused due to shuttle effect of active material, improve battery coulombic efficiency and
Cyclical stability.
Organogel is calcined at high temperature can form carbon skeleton, and influence of the calcining heat to carbon skeleton is very big, works as calcining
When temperature is higher, then carbon skeleton is destroyed, and when calcining heat is relatively low, then cause gel can not carbonization, residual is a large amount of
Organic matter, not only influence the electric conductivity of material, it is also larger on the influence of the capacitance of material, reduce the battery capacity of material,
Accordingly, it would be desirable to by many experiments to determine calcination time and calcining heat, it is preferred that 3.5~4.5h of calcining, calcining heat is
350~420 DEG C.
The lithium source is the electric matter of lithium, the oxide of lithium, lithium salts and the alkali containing lithium, specifically, the lithium source is lithium, hydroxide
At least one of lithium, lithium carbonate, lithium bicarbonate, lithium chloride, lithium acetate, lithium phosphate and lithium nitrate.
The ferrophosphorus source is that ferrous pyrophosphate and/or phosphoric acid hydrogen are ferrous.
According to the present invention, the content in lithium source and ferrophosphorus source is influence product LiCo1-xMxPO4The key factor of appearance structure,
It is preferred that, in step (3), the mol ratio in the lithium source and ferrophosphorus source is 1：(0.8~1.2).
Hydrothermal reaction condition be influence product structure key factor, it is preferred that the temperature of the hydro-thermal reaction be 120~
150 DEG C, the hydro-thermal reaction time is 5.5~7h.
A kind of lithium ion battery, including positive pole, barrier film, electrolyte and negative pole, it is described including positive active material, conductive agent
And binding agent, it is characterised in that the positive active material is above-mentioned composite positive pole.
The conductive agent can be well known to the art personnel, and the conductive agent is graphene, CNT, led
At least one of electro-graphitic.The binding agent can be well known to the art personnel, and the binding agent can be inclined
Polytetrafluoroethylene (PTFE) or polytetrafluoroethylene (PTFE).
By above-mentioned technical proposal, the present invention has following technique effect：
1st, modified polyorganosiloxane and LiCo are passed through1-xMxPO4/ C is combined, and is reduced corrosion of the electrolyte to positive electrode and is made
With so as to improve the stability and cycle life of battery；
2、LiCo1-xMxPO4With higher theoretical electric capacity, also cause lithium battery that there is higher specific capacitance；
3rd, by by three-dimensional carbon skeleton and LiCo1-xMxPO4It is compound to be effectively improved LiCo1-xMxPO4In charge and discharge process
The volumetric expansion of generation, hole can also provide passage for the migration of electronics and ion, and its larger specific surface area can
For LiCo1-xMxPO4Attachment point is provided, the loss that active material is caused due to shuttle effect is reduced, improves the coulombic efficiency of battery
And cyclical stability.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.
The present invention will be described in detail by way of examples below.
Embodiment 1
0.1mol cobalt nitrates and 0.3mol 2-methylimidazoles are reacted in the 20mL aqueous solution, complex solution is obtained, by network
Solution is closed in DMA is dissolved in, to be warming up to Isosorbide-5-Nitrae-two [(3,4- bis- octyloxy benzene)-connection amide groups] benzene
50 DEG C, stirring obtains organosol to dissolving, after being well mixed, and continues to stir 30min, is aged 6h, obtains cobalt-Isosorbide-5-Nitrae-two
[(the octyloxy benzene of 3,4- bis-)-connection amide groups] benzene gel；
Cobalt-Isosorbide-5-Nitrae-two [(3,4- bis- octyloxy benzene)-connection amide groups] benzene gel is calcined in argon gas, calcining heat is
350 DEG C, calcination time is 3.5h, obtains cobalt/carbon skeleton；
By 0.1mol lithium hydroxides, 0.1mol cobalt nitrates, 0.05mol nickel nitrates, 0.1mol phosphoric acid hydrogen ferrous iron in 50mL water
In stir, obtain mixed solution, then cobalt/carbon skeleton and mixed solution be transferred in reactor, water-filling is entered at 140 DEG C
LiCo is obtained after thermal response, reaction 6h0.66Ni0.34PO4/C。
By 96 parts by weight LiCo0.66Ni0.34PO4The poly- tetramethyl tetravinyl cyclosiloxane of/C, 4 parts by weight, 4 parts by weight are gathered
Vinylidene fluoride (PVDF), 4 parts by weight acetylene blacks are added in 50 parts by weight 1-METHYLPYRROLIDONEs (NMP), then in vacuum
Stirring forms uniform anode sizing agent in mixer.
The slurry is uniformly coated to wide 400mm, on thick 20 μm of aluminium foils, then 120 DEG C of drying, in 1.6MPa pressure
Cutting obtains the positive pole that size is 385mm × 42mm × 135 μm on cutting machine after lower roll-in.
(2) preparation of negative pole
100 parts by weight native graphites, 4 parts by weight polytetrafluoroethylene (PTFE) (PTFE), 4 parts by weight of carbon black per are added to 45 parts by weight
In dimethyl sulfoxide (DMSO), then stirring forms stable, homogeneous cathode size in de-airing mixer.
The slurry is uniformly coated to wide 400mm, on thick 10 μm of copper foil, in cutting after 120 DEG C of drying, rollings
Cutting obtains the negative pole that size is 43mm × 355mm × 135 μm on machine.
(3) assembling of battery
By LiPF6LiPF is configured to ethylene carbonate (EC) and diethyl carbonate (DEC)6Concentration is 1.0 mol/Ls
(wherein, EC and DEC volume ratio is 1 to solution：1) nonaqueous electrolytic solution, is obtained.Positive pole, the membrane layer polyethylene that (1) is obtained
(PE), the negative pole that (2) are obtained is laminated the electrode group for being wound into scroll with up- coiler successively, and obtained electrode group is put into one end
In the battery case of opening, and above-mentioned nonaqueous electrolytic solution is injected with 3.8g/Ah amount, lithium battery A1 is made after sealing.
Embodiment 2
(1) preparation of positive pole
By polyvinylpyrrolidone in dissolving water, stirring obtains organosol to dissolving；By 0.1mol cobaltous sulfates and
0.2mol 1,10- phenanthrolene react in 20mL water, obtain complex solution, by complex solution and polyvinylpyrrolidone
Mixed in N-methyl pyrrolidones, be warming up to 80 DEG C, stir 35min, be aged 3h, obtain cobalt-polyvinylpyrrolidone gel；
Cobalt-polyvinylpyrrolidone gel is calcined in argon gas, calcining heat is 380 DEG C, and calcination time is 4h, is obtained
Cobalt/carbon skeleton；
By 0.03mol lithium phosphates, 0.075mol cobaltous sulfates, 0.025mol zinc sulfate and 0.8mol ferrophosphorus source in 50mL water
Stir, obtain mixed solution, then cobalt/carbon skeleton and mixed solution are transferred in reactor, hydro-thermal is carried out at 150 DEG C
LiCo is obtained after reaction, reaction 5.5h0.75Zn0.25PO4/C。
By 96 parts by weight LiCo0.75Zn0.25PO4/ C, 4 parts by weight PSIs grafting dimethyl siloxane, 4
Parts by weight polyvinylidene fluoride (PVDF), 4 parts by weight acetylene blacks are added in 50 parts by weight 1-METHYLPYRROLIDONEs (NMP), so
Stirring forms uniform anode sizing agent in de-airing mixer afterwards.
The slurry is uniformly coated to wide 400mm, on thick 20 μm of aluminium foils, then 120 DEG C of drying, in 1.6MPa pressure
Cutting obtains the positive pole that size is 385mm × 42mm × 135 μm on cutting machine after lower roll-in.
(2) the preparation be the same as Example 1 of negative pole.
(3) the assembling be the same as Example 1 of battery.
Embodiment 3
0.1mol cobalt acetates and 0.4mol ethylenediamines are reacted in 20mL water, complex solution is obtained, by complex solution with
There is N- (3,4- methoxybenzoyl base)-N '-(4 '-nitro benzoyl) hydrazine in two methylene sulfones are dissolved in, to be stirred at 60 DEG C
50min is mixed, 10h is aged, obtains cobalt N- (3,4- methoxybenzoyl base)-N '-(4 '-nitro benzoyl) hydrazine gel；
Cobalt-N- (3,4- methoxybenzoyl base)-N '-(4 '-nitro benzoyl) hydrazine gel is calcined in nitrogen, forged
It is 400 DEG C to burn temperature, and calcination time is 4h, obtains cobalt/carbon skeleton；
By 0.1mol lithium nitrates, 0.08mol cobalt acetates, 0.02mol manganese acetates and 0.12mol phosphoric acid hydrogen ferrous iron in 50mL water
In stir, obtain mixed solution, then cobalt/carbon skeleton and mixed solution be transferred in reactor, water-filling is entered at 120 DEG C
LiCo is obtained after thermal response, reaction 7h0.8Mn0.2PO4/C。
By 95 parts by weight LiCo0.8Mn0.2PO4The poly- diphenyldimethyl siloxanes of/C, 5 parts by weight, 4 parts by weight gather inclined difluoro
Ethene (PVDF), 4 parts by weight acetylene blacks are added in 50 parts by weight 1-METHYLPYRROLIDONEs (NMP), then in de-airing mixer
Middle stirring forms uniform anode sizing agent.
The slurry is uniformly coated to wide 400mm, on thick 20 μm of aluminium foils, then 120 DEG C of drying, in 1.6MPa pressure
Cutting obtains the positive pole that size is 385mm × 42mm × 135 μm on cutting machine after lower roll-in.
(2) the preparation be the same as Example 1 of negative pole.
(3) the assembling be the same as Example 1 of battery.
Embodiment 4
0.2mol cobalt nitrates and 0.3mol oxalic acid are reacted in 20mL water, complex solution is obtained, by complex solution and N-
(3,5- methoxyl group base benzoyl)-N '-(4 '-cyanobenzoyl) hydrazine is mixed in n-butanol, is stirred at 75 DEG C
45min, is aged 24h, obtains cobalt-N- (3,5- methoxyl group base benzoyl)-N '-(4 '-cyanobenzoyl) hydrazine gel；
Cobalt-N- (3,5- methoxyl group base benzoyl)-N '-(4 '-cyanobenzoyl) hydrazine gel is calcined in nitrogen,
Calcining heat is 350 DEG C, and calcination time is 4.5h, obtains cobalt/carbon skeleton；
By 0.1mol lithium carbonates, 0.06mol cobalt nitrates, 0.04mol ferric nitrates and 0.12mol ferrous pyrophosphates in 50mL water
In stir, obtain mixed solution, then cobalt/carbon skeleton and mixed solution be transferred in reactor, water-filling is entered at 120 DEG C
LiCo is obtained after thermal response, reaction 5h0.6Fe0.4PO4/C。
By 98 parts by weight LiCo0.6Fe0.4PO4/ C, 2 parts by weight poly- N, N- diphenyltetramethyl ring disiloxane, 4 parts by weight
Polyvinylidene fluoride (PVDF), 4 parts by weight acetylene blacks are added in 50 parts by weight 1-METHYLPYRROLIDONEs (NMP), then true
Stirring forms uniform anode sizing agent in empty mixer.
The slurry is uniformly coated to wide 400mm, on thick 20 μm of aluminium foils, then 120 DEG C of drying, in 1.6MPa pressure
Cutting obtains the positive pole that size is 385mm × 42mm × 135 μm on cutting machine after lower roll-in.
(2) the preparation be the same as Example 1 of negative pole.
(3) the assembling be the same as Example 1 of battery.
Embodiment 5
By 0.2mol cobalt chlorides and 0.2mol 2,2- bipyridyls react in 20mL water, obtain complex solution, will be complexed molten
Liquid is mixed with Isosorbide-5-Nitrae-two [(3,4- bis- octyloxy benzene)-connection amide groups] benzene in DMA, in 68 DEG C of stirrings
45min, is aged 12h, obtains cobalt-Isosorbide-5-Nitrae-two [(3,4- bis- octyloxy benzene)-connection amide groups] benzene gel；
Cobalt-Isosorbide-5-Nitrae-two [(3,4- bis- octyloxy benzene)-connection amide groups] benzene gel is calcined in nitrogen, calcining heat is
420 DEG C, calcination time is 3.5h, obtains cobalt/carbon skeleton；
By 0.1mol lithium sources, 0.05mol cobalt chlorides, 0.05mol manganese chlorides and 0.1mol ferrous pyrophosphates in 50mL water
Stir, obtain mixed solution, then cobalt/carbon skeleton and mixed solution are transferred in reactor, hydro-thermal is carried out at 130 DEG C
LiCo is obtained after reaction, reaction 6.5h0.5Mn0.5PO4/C。
By 92 parts by weight LiCo0.5Mn0.5PO4/ C, 8 parts of poly- tetramethyl tetravinyl cyclosiloxanes, 4 parts by weight gather inclined difluoro
Ethene (PVDF), 4 parts by weight acetylene blacks are added in 50 parts by weight 1-METHYLPYRROLIDONEs (NMP), then in de-airing mixer
Middle stirring forms uniform anode sizing agent.
The slurry is uniformly coated to wide 400mm, on thick 20 μm of aluminium foils, then 120 DEG C of drying, in 1.6MPa pressure
Cutting obtains the positive pole that size is 385mm × 42mm × 135 μm on cutting machine after lower roll-in.
(2) the preparation be the same as Example 1 of negative pole.
(3) the assembling be the same as Example 1 of battery.
Comparative example 1：
According to the method for embodiment 1, unlike, in the preparation, directly prepare LiCo0.66Ni0.34PO4。
Comparative example 2：
According to the method for embodiment 1, unlike, do not contain poly- tetramethyl tetravinyl cyclosiloxane.
Performance test
Lithium battery and comparative example 1-2 that embodiment 1-5 is obtained are determined using following battery capacity method of testing respectively
The charge/discharge capacity of obtained lithium battery.As a result it is as shown in table 1.
Battery capacity method of testing：Charged with constant voltage charging method, limitation electric current is 0.1C (65mA), final voltage
For 4.4 volts；Discharged in constant-current discharge mode, discharge current is 1C (650mA), and the blanking voltage of electric discharge is 3.0 volts.
Table 1
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means.In order to avoid not
Necessary repetition, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (8)
1. a kind of composite positive pole, it is characterised in that including following material：Modified polyorganosiloxane and LiCo1-xMxPO4/C；
The M is at least one of Fe, Mn, Ni, Zn, Mo, Ti, Mg.
2. composite positive pole according to claim 1, it is characterised in that include the material of following parts by weight：LiCo1- xMxPO4The parts by weight of/C 92~98, the parts by weight of modified polyorganosiloxane 2~8.
3. composite positive pole according to claim 1 or 2, it is characterised in that the modified polyorganosiloxane is poly- tetramethyl
Base tetravinyl cyclosiloxane, poly- diphenyldimethyl siloxanes, PSI are grafted dimethyl siloxane and poly-
At least one of N, N- diphenyltetramethyl ring disiloxane.
4. the preparation method of the composite positive pole according to any one in claims 1 to 3, it is characterised in that including
Following steps：
(1) cobalt source and ligand reaction are generated into metal complex, then metal complex with gelator is mixed equal in a solvent
Even, ageing obtains plural gel；
(2) plural gel is calcined into 3.5~4.5h in inert gas, calcining heat is 350~420 DEG C, obtains calcined product；
(3) lithium source, ferrophosphorus source, cobalt source, M sources and calcined product are subjected to hydro-thermal reaction in aqueous, obtain LiCo1-xMxPO4/
C；
(4) by LiCo1-xMxPO4After/C, modified polyorganosiloxane are mixed in proportion, composite positive pole is obtained；
Wherein, the M is at least one of Fe, Mn, Ni, Zn, Mo, Ti, Mg；The part be 2-methylimidazole, pyridine, 2,
One kind in 2- bipyridyls.
5. composite positive pole according to claim 4, wherein, in step (1), the organogel factor is pasted for ring
Smart derivative, cholesteryl anthraquinone-2-carboxylic acid, benzyl carbamide derivative, 2- octyldodecyls 4- [(naphthalidine) carboxyl amine]
Benzoic ether, 1,4- bis- [(the octyloxy benzene of 3,4- bis-)-connection amide groups] benzene, N- (3,4- alkoxybenzoyls)-N '-(4 '-nitre
Base benzoyl) hydrazine, at least one of N- (3,5- alkoxybenzoyls)-N '-(4 '-cyanobenzoyl) hydrazine.
6. the preparation method of composite positive pole according to claim 4, wherein, in step (3), the lithium source and phosphorus
The mol ratio of source of iron is 1：(0.8~1.2).
7. the preparation method of composite positive pole according to claim 1, wherein, the temperature of the hydro-thermal reaction is 120
~150 DEG C, the hydro-thermal reaction time is 5.5~7h.
8. a kind of lithium ion battery, including positive pole, barrier film, electrolyte and negative pole, it is described including positive active material, conductive agent and
Binding agent, it is characterised in that the positive active material is the composite positive pole described in claims 1 to 3 any one.
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