CN103259004B - Anode material for liquid-state and semi-liquid-state metal energy-storing batteries - Google Patents

Abstract

The invention provides an anode material for liquid-state and semi-liquid-state metal energy-storing batteries, belongs to an electrode material of an energy-storing battery, and solves the problems that the operation temperature is high, the working voltage is low, the corrosion is strong and the pollution to the environment is caused in an existing liquid-state metal battery. The anode material is Sn alloy formed by metal Sn or the Sn and one or more than one monomer of Sb, Pb, Bi and Te. The metal Sn or the Sn alloy is used as the anode material, the smelting point of the metal Sn is low (231.9 DEG C) and the metal Sn has no environmental pollution; the Sn alloy is simple to prepare and is low in cost; the metal Sn, the Sn alloy and an existing cathode material have the good alloy performance and have stability under a high temperature; when the metal Sn and the Sn alloy are applied to a liquid-state metal battery and a semi-liquid-state double-metal battery, the operation temperature can be lowered, the maintenance cost can be reduced, the voltage of the battery can be increased or stabilized, the large-current and high-density charging/discharging performance of the battery is improved, and the service life of the battery is prolonged.

Description

For positive electrode that is liquid and semi-liquid metal energy-storage battery

Technical field

The invention belongs to the electrode material of energy-storage battery, be specifically related to a class for positive electrode that is liquid and semi-liquid metal battery.

Background technology

The development and utilization of the regenerative resource such as wind energy and solar energy is the focus that energy field is paid close attention to always, but wind energy and the effectively grid-connected of solar power generation still also exist very large challenge at present, and extensive energy storage is one of key technology of this challenge of reply.Therefore, the research and development of the extensive energy-storage battery system of high efficiency low cost in recent years become the focus in electrochemical energy storage field, as modification lead-acid battery, and lithium ion battery, sodium-sulphur battery etc.But particularly price and life-span etc. all cannot meet the current energy storage market demand to the multinomial energy storage parameter of current electrochemical energy storage technology.For sodium-sulphur battery relatively more good at present and all-vanadium flow battery energy storage technology, its mature technology cost of investment is about 3000 yuan/kWh and 5000 yuan/kWh respectively, also has larger gap from market expectations (1500 yuan/kWh).

In recent years, the team that Massachusetts Institute Technology D.R.Sadoway teaches proposes the new ideas that " full liquid metal cell " (Liquid Metal Battery) is applied to the extensive energy storage of electrical network.The essential characteristic of full liquid metal cell is: battery plus-negative plate is formed by cheap metal material, electrolyte is simple inorganic salts, battery is 300 DEG C ~ 700 DEG C operations, during operation, both positive and negative polarity metal and electrolyte are all liquid, due to molten salt electrolyte, positive pole, and negative pole liquid metal is immiscible and density is different, three layers of liquid AUTOMATIC ZONING.On this conceptual foundation, this team reported the full liquid metal energy-storage battery be made up of the magnesium of cheapness (negative pole) and antimony (positive pole) in 2012 in the article at " JACS " (Journal of the American Chemical Society) " Magnesium-Antimony Liquid Metal Battery for Stationary Energy Storage ".The excellent energy storage characteristics such as test shows, this battery has at the bottom of cost, and the life-span is long, and structure is simple, easy amplification are the very potential novel energy storage cell technology of one.

But the fusing point of magnesium and antimony is higher, be respectively 650 DEG C and 631 DEG C.In order to meet the designing requirement of its " full liquid metal cell ", the operating temperature of this battery need more than 700 DEG C; The discharge voltage of this battery is lower, approximately only has 0.4V; And cell performance decay is very fast during hot operation; Meanwhile, liquid antimony alloy has stronger corrosivity, forms complicated intermetallic compound easily cause battery short circuit with negative metal; And the impact of antimony metal on environment limits its large-area popularization.

Summary of the invention

The invention provides a class for positive electrode that is liquid and semi-liquid metal battery, solve existing liquid metal cell operating temperature high, operating voltage is low, and corrosivity by force and the problem of environmental pollution.

Provided by the present invention for positive electrode that is liquid and semi-liquid metal battery, it is characterized in that:

It is the Sn alloy that the one or more than one simple substance in metal Sn and Sb, Pb, Bi, Te is formed, and its molar percentage is:

Sn _{50 ~ 90}sb _{50 ~ 10}, Sn _{50 ~ 90}pb _{50 ~ 10}, Sn _{50 ~ 90}bi _{50 ~ 10}, Sn _{75 ~ 90}te _{25 ~ 10}, Sn _{50 ~ 90}sb _{1.8 ~ 9}pb _{41 ~ 4}, Sn _{50 ~ 90}sb _{1 ~ 27.5}bi _{45 ~ 4.5}, Sn _{75 ~ 90}sb _{20.5 ~ 6.3}te _{1.8 ~ 9.25}, Sn _{50 ~ 90}pb _{0.1 ~ 49.5}bi _{49.5 ~ 0.1}, Sn _{50 ~ 90}pb _{49.5 ~ 9}te _{0.1 ~ 5}, Sn _{75 ~ 90}bi _{6.5 ~ 24.5}te _{0.2 ~ 8.75}, wherein each component molar percentage is added and equals 100%.

Adopt metal electrode energy-storage battery of the present invention, comprise housing, positive pole, electrolyte, negative pole and current collector, described housing is the metal cylinder of bottom end closure, metal cylinder barrel applies dielectric ceramic layer or in metal cylinder, installs insulating ceramics pipe additional, sequentially put from bottom to top in dielectric ceramic layer or in insulating ceramics pipe and have positive pole, electrolyte and negative pole, flat current collector is enclosed with in negative pole, described housing upper surface is by top closure, the negative wire be connected with described current collector passes the centre bore of top cover and insulate with top cover, described current collector is porous foam metal material.

Method for preparing anode material provided by the present invention is simple; when it is Sn alloy; with described molar ratio weighing metal Sn and raw materials; ceramic crucible or metallic crucible is put into after mechanical mixture; the crucible filling compound is put in heating furnace; under vacuum or inert gas shielding condition, carry out alloying reaction, can alloy material be obtained.

Directly positive electrode can also be processed in metal battery case; when it is Sn alloy; with described molar ratio weighing metal Sn and raw materials; metal battery case positive pole position is put into after mechanical mixture; again described raw material and metal battery case are put in heating furnace, under vacuum or inert gas shielding condition, carry out alloying reaction, make positive pole; after part such as assembling negative pole, electrolyte etc., carry out metal battery test.

Test shows, existing liquid state/semi-liquid metal cell negative electrode material is generally Li, Na, K, Ca, Mg or their alloy, first, the simple substance of the one or more than one in metal Sn and Sb, Pb, Bi, Te has wider alloying scope, namely under wider proportion, also seldom there is high-melting-point alloy phase, if the fusing point of the arbitrary proportion alloy phase of Sn and Pb is all below 330 DEG C; Secondly, metal Sn of the present invention or Sn alloy can with negative material alloying preferably, as can Li be reached at the temperature of Sn and Li only below 500 DEG C _{(0 ~ 55mol%)}the alloys range of Sn; The utilance of the positive electrode therefore in the present invention is higher, can reduce battery cost; 3rd, the research of applicant shows, Sn alloy material can improve charge-discharge performance, the extending battery life of battery, and after SnSb alloy material and negative material form electrode, its test result shows that efficiency for charge-discharge is that about 60% of positive pole brings up to more than 70% by metal Sn; And Sn alloy material can improve the voltage performance of battery, after SnSb alloy material and negative material form battery, operating voltage can be brought up to 0.7 ~ 0.8V by the 0.6V of metal Sn as positive pole and had wider discharge platform, improve the voltage efficiency of battery.

In sum, the present invention using metal Sn or Sn alloy as positive electrode, metal Sn fusing point low (231.9 DEG C), non-environmental-pollution, Sn reasonable offer is simple, with low cost; The two and existing negative material have good alloy property, at high temperature there is stability, operating temperature can be reduced when making them be applied in " liquid metal cell " and " semi liquid state bimetallic cell ", reduce maintenance cost, improve or stable cell voltage, improve battery big current, high density charge-discharge performance, extending battery life.

Accompanying drawing explanation

Fig. 1 adopts metal electrode energy-storage battery cross-sectional view of the present invention;

Fig. 2 is the charge-discharge performance curve of the metal electrode energy-storage battery adopting embodiment 32;

Fig. 3 is the metal electrode energy-storage battery discharge performance curve adopting embodiment 32;

Fig. 4 is the metal electrode energy-storage battery charge-discharge performance curve adopting embodiment 33;

Fig. 5 is the discharge performance curve under the different current density of metal electrode energy-storage battery of employing embodiment 33.

Embodiment

Below in conjunction with drawings and Examples, the present invention is further described.

Table 1 lists 36 embodiments of the present invention, adopt the metal electrode energy-storage battery of each embodiment as shown in Figure 1, comprise housing 1, positive pole 3, electrolyte 4, negative pole 5 and current collector 6, described housing 1 is the metal cylinder of bottom end closure, metal cylinder barrel applies dielectric ceramic layer or in metal cylinder, installs insulating ceramics pipe 2 additional, sequentially put from bottom to top in dielectric ceramic layer or in insulating ceramics pipe 2 and have positive pole 3, electrolyte 4 and negative pole 5, flat current collector 6 is enclosed with in negative pole 5, described housing 1 upper surface is closed by top cover 7, the negative wire 8 be connected with described current collector 6 passes the centre bore of top cover 7 and insulate with top cover, described current collector 6 is porous foam metal material.

Each embodiment is formed " liquid metal cell " and " Semi-liquid metal electrode energy storage battery " with multiple negative material and electrolyte respectively as positive electrode and its performance is tested, wherein electrolyte is the blend of inorganic salt mixt or inorganic salt mixt and ceramic powders, in the case of the latter, ceramic powders in the electrolyte shared mass percent be 10% ~ 60%; Test result is as shown in table 1:

Table 1

Adopt Sn metal positive-pole material of the present invention, the battery operating temperature in embodiment 1 ~ 19 and embodiment 32,34 all far below comparative example in the working temperature of battery, embodiment 2 ~ 5,17, battery operating temperature in embodiment 34 is all lower than 500 DEG C; The operating voltage of the batteries such as embodiment 22 ~ 23, embodiment 27 ~ 28 all higher than 0.75V, far above the operating voltage of comparative example battery.

Fig. 2 is the charge-discharge performance curve of the metal electrode energy-storage battery adopting embodiment 32; Its charging/discharging voltage is respectively about 0.7V and 0.6V, and voltage efficiency is higher.

Fig. 3 is the metal electrode energy-storage battery discharge performance curve adopting embodiment 32; As can be seen from the figure battery is at 0.1Acm ^-2current density under circulation 25 weeks, discharge capacity is more steady between 5Ah ~ 9Ah.

Fig. 4 is the metal electrode energy-storage battery charge-discharge performance curve adopting embodiment 33; As we know from the figure, its charging voltage is stabilized in about 1.06V, and discharge voltage is stabilized in about 0.7V.

Fig. 5 is the discharge performance curve under the different current density of metal electrode energy-storage battery of employing embodiment 33.As can be seen from the figure battery is at 0.1Acm ^-2and 0.2Acm ^-2current density under, after circulation 20 weeks, capacity is down to 35Ah and 20Ah from 40Ah and 30Ah respectively, and capability retention is higher, is respectively 90% and 66.7%.

Test result shows: electrode material of the present invention is used for reducing cell operating temperature in liquid metal cell and Semi-liquid metal electrode energy storage battery, obtain good voltage performance, effectively extend the energy storage life-span of battery and reduce the energy storage cost of battery.

Claims (1)

1., for a positive electrode that is liquid and semi-liquid metal battery, it is characterized in that:

It is the Sn alloy that the one or more than one simple substance in metal Sn and Sb, Pb, Bi, Te is formed, and its molar percentage is:

Sn _{50 ~ 90}sb _{50 ~ 10}, Sn _{50 ~ 90}pb _{50 ~ 10}, Sn _{50 ~ 90}bi _{50 ~ 10}, Sn _{75 ~ 90}te _{25 ~ 10}, Sn _{50 ~ 90}sb _{1.8 ~ 9}pb _{41 ~ 4}, Sn _{50 ~ 90}sb _{1 ~ 27.5}bi _{45 ~ 4.5}, Sn _{75 ~ 90}sb _{20.5 ~ 6.3}te _{1.8 ~ 9.25}, Sn _{50 ~ 90}pb _{0.1 ~ 49.5}bi _{49.5 ~ 0.1}, Sn _{50 ~ 90}pb _{49.5 ~ 9}te _{0.1 ~ 5}, Sn _{75 ~ 90}bi _{6.5 ~ 24.5}te _{0.2 ~ 8.75}, wherein each component molar percentage is added and equals 100%.